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Battle of Wagram
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Battle of Wagram
exaggerated and more realistic estimates place the number of guns at either 72, 80 or 84. André Masséna, a highly credible source and also a man who was in the vicinity of the battery at the time when it was deployed, places its complement at 84 pieces: 60 pieces of the Guard artillery and 24 of the "Army of Italy". Despite claims from some authors that the cannon of the Bavarian division were also a part of the battery, there is actually no source contemporary to the battle supporting that claim.
- MacDonald's Corps included Jean-Baptiste Broussier's 1st division, 10 battalions and 4,400 men strong, which had not seen any action during 5 July fighting. It also included Jean Maximilien Lamarque's
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2nd Division, which on 4 July numbered 11 battalions, with some 3,740 men, but which had seen intense action during the night attacks on 5 July and had taken casualties.
- The general retreat direction was northwest. Rosenberg's troops were already retreating north towards Bockfluss. Charles's orders provided that the various army corps will retreat, following the pace set by Bellegarde's I Korps. The order provided that Bellegarde was to move towards Gerasdorf, Liechtenstein's cavalry was to remain in the Gerasdorf plain, sending patrols towards the Russbach river to collect information about the French advance, Liechtenstein's grenadiers were directed to Hagenbrunn, Kollowrat's III Korps
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was to move towards the Stammersdorf heights, while Klenau was to deploy between Gerasdorf and Leopoldsau. Charles informed his corps commanders that he would be establishing his headquarters at Stammersdorf, and that they were all required to send an officer there before nightfall, in order to receive new orders.
# External links.
- Website of the Museum of the Battle of Wagram in Deutsch-Wagram (German Language)
# Bibliography.
- David Chandler, "Napoleon's Marshals", Weidenfeld & Nicolson, London, 1998, pp 247–251.
- Bowden, Scotty & Tarbox, Charlie. "Armies on the Danube 1809". Arlington, Texas: Empire Games Press, 1980.
- Gill, John H. "1809: Thunder on the Danube". 3 Volumes, Frontline
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Stammersdorf heights, while Klenau was to deploy between Gerasdorf and Leopoldsau. Charles informed his corps commanders that he would be establishing his headquarters at Stammersdorf, and that they were all required to send an officer there before nightfall, in order to receive new orders.
# External links.
- Website of the Museum of the Battle of Wagram in Deutsch-Wagram (German Language)
# Bibliography.
- David Chandler, "Napoleon's Marshals", Weidenfeld & Nicolson, London, 1998, pp 247–251.
- Bowden, Scotty & Tarbox, Charlie. "Armies on the Danube 1809". Arlington, Texas: Empire Games Press, 1980.
- Gill, John H. "1809: Thunder on the Danube". 3 Volumes, Frontline Books, 2007–2011
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Shang-Chi
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Shang-Chi
Shang-Chi
Shang-Chi () is a fictional superhero appearing in American comic books published by Marvel Comics. The character was created by writer Steve Englehart and artist Jim Starlin, first appearing in "Special Marvel Edition" #15 (cover-dated December 1973) in the Bronze Age of Comic Books. Often referred to as the "Master of Kung Fu", Shang-Chi is proficient in numerous unarmed and weaponry-based wushu styles, including the use of the "gùn", "nunchaku", and "jian". In later years, he gains the power to create countless duplicates of himself, and joins the Avengers.
Shang-Chi was spun off from novelist Sax Rohmer's licensed property as the unknown son of fictional villain Fu Manchu. In
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later editions, his connection to Fu was underplayed after Marvel lost the comic book rights to the latter's character.
Shang-Chi is set to make his live-action debut in the upcoming film "Shang-Chi and the Legend of the Ten Rings" (2021), set within the Marvel Cinematic Universe. He will be played by Canadian actor Simu Liu.
# Publication history.
The character was conceived in late 1972. Marvel had wished to acquire the rights to adapt the "Kung Fu" television program, but were denied permission by the show's owner, Warner Communications, owner of Marvel's primary rival, DC Comics. Instead, Marvel acquired the comic book rights to Sax Rohmer's pulp villain Dr. Fu Manchu. They developed
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Shang-Chi, a master of kung fu, who was introduced as a previously unknown son of Fu Manchu. Though an original character himself, many of Shang-Chi's supporting characters (most notably Fu Manchu, Sir Denis Nayland Smith, Dr. James Petrie and Fah Lo Suee) were Rohmer creations. No characters from the "Kung Fu" television series carried over into the comic series, though the character Lu Sung, in an early issue, bears a strong resemblance to Kwai Chang Caine with the addition of a moustache. With artist Paul Gulacy, his visual appearance was modeled after that of Bruce Lee.
Shang-Chi first appeared in "Special Marvel Edition" #15 (December 1973) by Steve Englehart and Jim Starlin. He appeared
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again in issue #16, and with issue #17 (April 1974) the title was changed to "The Hands of Shang-Chi: Master of Kung Fu". Amidst the martial arts craze in the United States in the 1970s, the book became very popular, surviving until issue #125 (June 1983), a run including four giant-size issues and an annual. "Special Collector's Edition" #1 (1975) cover-titled as "Savage Fists of Kung Fu" reprinted stories from "The Deadly Hands of Kung Fu" #1-2; "The Deadly Hands of Kung Fu Special" #1; and "Special Marvel Edition" #15. He did several crossovers with other Marvel martial artists, including the White Tiger, Iron Fist and the Daughters of the Dragon (Colleen Wing and Misty Knight). He appeared
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regularly in "The Deadly Hands of Kung Fu".
Shang-Chi had two more short series: the "Master of Kung Fu: Bleeding Black" one-shot (1990) and the MAX miniseries "Master of Kung Fu: Hellfire Apocalypse" (2002) with artist Paul Gulacy on art again. The character had two stories in the anthology series "Marvel Comics Presents", including one by Moench that ran in the series' first eight issues in 1988, and co-starred in the "Moon Knight Special" (1992). In 1997 a story arc starring Shang-Chi ran in "Journey into Mystery" #514-516, and was intended to lead into a miniseries for the character in 1998.
Although spun out of licensed properties, Shang-Chi is a Marvel-owned character and has been firmly
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established as a part of the Marvel Universe with guest appearances in numerous other titles, such as "Marvel Team-Up", "Marvel Knights" and "X-Men". Most of the original, licensed characters in the supporting cast have been either phased out or renamed in the more recent series and stories.
In some of his modern appearances, mention is made of his villainous father either in cryptic terms or using a variety of new names, due to Marvel no longer having the rights to Fu Manchu. In 2010's "Secret Avengers" #6-10, writer Ed Brubaker officially sidestepped the entire issue via a storyline where the Shadow Council resurrects a zombified version of Fu Manchu, only to discover that "Fu Manchu" was
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only an alias and that Shang-Chi's father real name was Zheng Zu, an ancient Chinese sorcerer who discovered the secret to immortality. Similarly, Shang-Chi's half sister Fah Lo Suee was later renamed Zheng Bao Yu / Cursed Lotus in 2013's "Fearless Defenders" #8 while Smith and Petrie have not appeared in any Marvel properties since the end of the "Master of Kung Fu" series in 1983.
Shang-Chi returned as a main character in the 2007 "Heroes for Hire" comic book.
# Fictional character biography.
## "Master of Kung Fu".
Shang-Chi was born in the Honan province of the People's Republic of China, and is the son of Fu Manchu, the Chinese mastermind who has repeatedly attempted world conquest
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and had a thirst for blood. His mother was a white American woman genetically selected by his father. Shang-Chi was raised and trained from infancy in the martial arts by his father and his tutors. Believing his father was a benevolent humanitarian, Shang-Chi was sent on a mission to London to murder Dr. James Petrie, who his father claimed was evil and a threat to peace. After successfully assassinating Petrie, he encountered Fu Manchu's archenemy, Sir Denis Nayland Smith, who revealed to Shang-Chi his father's true nature. After confronting his mother in New York City for the truth, Shang-Chi realized that Fu Manchu was evil. Shang-Chi fought his way past Fu Manchu's Si-Fan assassins at his
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Manhattan headquarters, telling his father that they were now enemies and vowing to put an end to his evil schemes. Shang-Chi subsequently fought his adoptive brother Midnight, who was sent by their father to kill Shang-Chi for his defection and then encountered Smith's aide-de-camp and MI-6 agent Black Jack Tarr, sent by Smith to apprehend Shang-Chi. After several encounters and coming to trust one another, Shang-Chi eventually became an ally of Sir Denis Nayland Smith and MI-6. Together with Smith, Tarr, fellow MI-6 agents Clive Reston and Leiko Wu, his eventual love interest, and Dr Petrie, who was revealed to still be alive, Shang-Chi went on many adventures and missions, usually thwarting
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his father's numerous plans for world domination.. Shang-Chi would occasionally encounter his half-sister Fah Lo Suee who led her own faction of the Si-Fan, but opposed her attempts to make him a pawn in her own schemes to usurp their father from his criminal empire.
With Smith, Tarr, Reston, Wu and Petrie, he formed Freelance Restorations, Ltd, an independent spy agency based in Stormhaven Castle, Scotland. After many skirmishes and battles, Shang-Chi finally witnessed the death of Fu Manchu. Not long after his father's death, a guilt-ridden Shang-Chi quit Freelance Restorations, cut ties with his former allies, forsook his life as an adventurer, and retired to a village in remote Yang-Tin,
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China, to live as a fisherman.
## Return.
Some time later, Shang-Chi returned from China and rejoined Tarr, Reston, and Wu. They battled Argus' terroristic group, formed to cause the United States to act more aggressively against all terrorists. In order to gain information, Argus had Wu tortured, cutting off her left hand as a message. She was rescued by Shang-Chi and the others, but not before he suffered a dose of a slow-acting poison. Before the poison could kill him, he was cured of its effects by Fu Manchu's elixir vitae.
After his father was revealed to still be alive, Shang-Chi would later assist his old allies (who had rejoined MI-6) against him and his previously unknown half-brother
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Moving Shadow. The mission was a success, resulting in his father's Hellfire weapon being destroyed and Moving Shadow's death at their father's hand for his failure in killing Shang-Chi.
## "Heroes for Hire".
As a member of the restored Heroes for Hire, Shang-Chi had put his strength of character at the service of their teammates. Humbug, turning against the heroes, tries to double cross both his friends and the "Earth Hive" of insects, joining the Hive, and offering Colleen Wing and Tarantula to a lifetime of tortures. Even so, when a dying Humbug begs his friend to mercy kill him, Shang-Chi refuses, until he finds that Humbug actually had no qualms to torture Tarantula, if it meant less
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suffering for Colleen. Shang-Chi then snaps his neck and leaves with the catatonic Tarantula, ashamed of what he believed he had to become, a soulless murderer.
Still working for MI-6, he goes on to collaborate with Pete Wisdom of MI-13 in facing the Welsh dragon, which had turned amnesiac and become a human crimelord. Shang-Chi had been told by Wisdom that the dragon (being inherently noble) would go free once it remembered its true origins, and was embittered to find this had been a lie. He became the tutor of a young Earth-616 Killraven.
## Heroic Age.
In the "Shadowland" storyline, Shang-Chi is one of the heroes fighting the Hand's ninjas. He later works together with Spider-Man against
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Mister Negative and temporarily takes Mister Negative's powers until Shang-Chi is brought back to normal by Spider-Man.
In "Secret Avengers", Steve Rogers tracks Shang-Chi down to help turn back the Shadow Council, which has partially resurrected Shang-Chi's father (who died sometime after their last encounter) and employed the Hai-Dai, a squad of assassins, to hunt Shang-Chi down. After further research, Beast reveals to Shang-Chi and the Secret Avengers that his father's true identity is that of an ancient sorcerer named Zheng Zu who gained immortality after stealing one of his brothers' life essence and that "Fu Manchu" was merely an alias. When Shang-Chi and Rogers meet with John Steele
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and the Shadow Council for the prisoner exchange for a captured Sharon Carter, Rogers is overpowered by Steele and Shang-Chi is captured. While Zheng Zu prepares to sacrifice Shang-Chi to complete his resurrection, the Avengers and Moon Knight drop in on the him and the Shadow Council. The Prince of Orphans disrupts the ritual, resulting in Zheng Zu's permanent death and Shang-Chi's rescue.
Per the instructions of the new Madame Web, Shang-Chi has begun training Spider-Man in kung fu to help him compensate for the recent loss of his spider-sense.
## "Marvel NOW!".
During the "Marvel NOW!" relaunch, Shang-Chi joins the Avengers after being recruited by Captain America and Iron Man.
When the
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Illuminati were exposed to have tampered with the mind of Captain America and attempting to destroy worlds threatening Earth as part of the Incursions as seen in the "Time Runs Out" storyline, Shang-Chi joined a faction of the Avengers led by Sunspot. Sunspot's Avengers, having taken control over A.I.M., discovered that "Incursion points" (points where an Incursion world that is about to hit Earth can be seen) were causing a massive number of physical mutations among those who stumbled upon the locations. Sending Shang-Chi to an incursion point in Japan, Shang-Chi was exposed to cosmic-level radiation that transformed Shang-Chi into a mutate capable of creating duplicates of himself.
While
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on a mission to capture Crossbones, Shang-Chi is informed by Captain America about his former lover Leiko Wu's murder at the hands of Razor Fist while working undercover for MI-6 in one of London's triads. Shang-Chi travels to London for Leiko's funeral and while wondering around Chinatown (where Leiko was murdered), he is attacked by unknown assailants, one whom reveals to Shang that the crime lord White Dragon was behind the murder. Shang-Chi is approached by triad clan leader and former enemy Skull-Crusher who offers him a truce; Chao Sina reveals he and Leiko became lovers while she was working undercover and had planned to defect from MI-6 for him. With help from Skull-Crusher and the newly
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arrived Daughters of the Dragon and the Sons of the Tiger, Shang-Chi confirms that Razor Fist was hired by White Dragon to kill Leiko due to her involvement with his rival clan leader Skull-Crusher and discovers that White Dragon has access to the Mao Shan Pai, a powerful Chinese black magic. Shang-Chi and Skull-Crusher infiltrate White Dragon's estate where they discover a room displaying the decapitated heads of missing triad leaders. The two of them fight White Dragon but are captured by Shang-Chi's brother, Midnight Sun, who reveals himself to be the true mastermind behind White Dragon. With the Mao Shan Pai spellbook taken by White Dragon's men, M'Nai plans to use its magic to give him
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power and influence over the triad clans, finally fulfilling Zheng Zu's legacy. Needing the heads of the clan leaders in order to complete the ritual, Midnight Sun beheads White Dragon and Skull-Crusher and proceeds to cast the spell. Instead of giving him power, the spell resurrects Leiko from Chao's spilled blood. The vengeful and black magic wielding Leiko reveals that Skull-Crusher made her the leader of his clan before her death; Chao's death made the ritual invalid and instead brought her back from the dead to punish Midnight Sun. Shang-Chi is able to knock out Midnight Sun during their fight while Leiko brutally defeats Razor Fist by ripping off his bladed arms. Leiko uses her newfound
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powers to summon the dead spirits of Skull-Crusher, White Dragon and the other dead triad leaders, who drag Midnight Sun into their realm. When Leiko attempts to execute a maimed Razor Fist, Shang-Chi pleads with his former lover to stop; while he is able to get Leiko to spare Razor Fist, he is unable to bring her back to her normal self. Black Jack Tarr (now director of MI-6) and his men raid the estate; Razor Fist and White Dragon's men are arrested while Leiko escapes. Before leaving London, Shang-Chi leaves a photo of him and Leiko at her grave, which is later taken by Leiko after he leaves.
## "The Protectors".
Shang-Chi joins several other Asian American superheroes (Hulk (Amadeus Cho),
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Silk, Ms. Marvel, Jimmy Woo, and S.H.I.E.L.D. agent Jake Oh) for a fundraiser in Flushing, Queens. Later while the group is spending the night out in Koreatown, Manhattan they are ambushed by the alien Prince Regent Phalkan and his small army from Seknarf Seven. Shang-Chi and his allies briefly fight off the invaders before they and a large group of bystanders are teleported near Seknarf Seven, where Phalkan demands that the group offer a few people for food within a time limit. Dubbing their group "The Protectors", Woo rallies the group and bystanders into working together to escape, while Shang-Chi leads an attack with Silk and Ms. Marvel. The Protectors are eventually able to free themselves
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and defeat Phalkan and his forces with the help of the bystanders. The Alpha Flight Space Program arrives to rescue the Protectors and bystanders and arrest Phalkan, who Sasquatch reveals was exiled from Seknarf Seven for treason.
## "Secret Empire".
During the "Secret Empire" storyline, Shang-Chi was found to have been a prisoner of HYDRA in Madripoor following HYDRA's takeover of the United States. After Hive and Gorgon are defeated, the Tony Stark A.I. finds him and he states that he does not have the Cosmic Cube shard anymore. A flashback revealed that Emma Frost took the Cosmic Cube shard from him when he was unconscious. Shang-Chi was later seen with the Underground when they and other
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superheroes are fighting HYDRA's forces in Washington, D.C.
## "Domino".
Seeking a way to fight her ability stealing adversary Topaz, Domino approaches Shang-Chi (who was referred to her by his Protectors teammate Amadeus Cho) at his retreat in Lantau Island for training. After a long training session, the two spend a romantic night out in Hong Kong, only to be ambushed at a night club by a large group of Shang-Chi's enemies, led by Midnight and including Razor Fist, Shen Kuei, Shockwave, Death-Hand, Shadow Stalker, Tiger-Claw and others. Domino and Shang-Chi defeat them with relative ease. The two are eventually confronted by Topaz who Domino defeats using Shang-Chi's teachings. Despite Shang-Chi's
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pleas for mercy, Domino kills Topaz. Disappointed, Shang-Chi breaks up with Domino and dismisses her as his student.
## "War of the Realms".
After taking part in a demonstration for Jimmy Woo's Pan-Asian School for the Unusually Gifted in Mumbai, Shang-Chi and the Protectors are offered membership to Jimmy's Agents of Atlas. Shang-Chi and the others are suddenly alerted by the news of Malekith's invasion of Earth; most of the New Agents of Atlas head to Seoul while Ms. Marvel joins Jake Oh and the Champions in New York. Shang-Chi and the others defend Seoul from Malekith's ally Queen Sindr and her Fire Goblin forces from Muspelheim with help from the Korean heroes White Fox, Crescent, Io and
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Luna Snow. After Sindr threatens to summon a volcano in the middle of the city and kill millions of innocents, Brawn teleports Atlas and their new allies away from the battle, allowing Sindr to peacefully annex South Korea. Brawn eventually summons the Chinese heroes Sword Master and Aero, Filipina heroine Wave, and the Hawaiian Goddess of Fire and Volcanoes Pele from Shanghai to help assist in the fight against Sindr. The newly summoned heroes are less than pleased for being taken out of their previous battle, but Pele quickly puts a stop to the infighting, warning the group that Sindr plans to melt the polar ice caps if they don't work together. When Sword Master continues to protest, Shang-Chi
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knocks him to the ground, surprising the young hero. After formulating a plan, Brawn confronts Sindr and her forces directly while Aero, Wave and Luna use Sindr's Black Bifrost to travel to the Arctic to decrease its temperature; Shang-Chi and the others are teleported to Atlas' ally Monkey King of the Ascendants in Northern China where Shang-Chi begins training the remaining members for their final fight. When Sun Wukong scoffs at the idea of being trained by a mortal, Shang-Chi disarms him, impressing the Monkey King. As planned by Brawn, the Queen of Cinders arrives in Northern China with a captured Brawn, only to be taken by surprise by Shang-Chi and the others, who defeat Sindr with Shang-Chi's
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training, although Pele (who is revealed to have been M-41 Zu, a mystically enhanced Atlas Android) and Monkey King sacrifice themselves in the process. Despite given the chance to surrender, Sindr flees using the Black Bifrost, only for Shang-Chi and the others to follow her with Brawn's teleporter, where they help Captain Marvel defeat her and her remaining forces at the Great Wall of China near Beijing. Shang-Chi is later shown fighting the remaining Fire Goblins alongside Wolverine, Hawkeye, Shuri and the Warriors Three in Shanghai. After Malekith's defeat, Shang-Chi is seen with the other Agents in Shanghai looking on while the captured Fire Goblins are escorted back to Muspelheim.
##
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New Agents of Atlas.
Shang-Chi officially joins the New Agents of Atlas. Shortly after the "War of the Realms" event, Shang-Chi encounters Sword Master in New York City, who is searching for his missing father. Noticing the upstart hero's inexperience and recklessness, Shang takes Lie under his wing to improve his skills. Unbeknownst to the two of them, they are being watched by Ares.
# Powers and abilities.
Although it has never been determined exactly how extensive Shang-Chi's fighting skills are, he has beaten numerous superhuman opponents. Shang-Chi is classed as an athlete but he is one of the best non-superhumans in martial arts and has dedicated much of his life to the art, being referred
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to by some as the greatest empty-handed fighter and practitioner of kung fu alive. Much of his physical abilities seem to stem from his mastery of chi, which often allows him to surpass physical limitations of normal athletes. He has also demonstrated the ability to dodge bullets from machine guns and sniper rifles, and is able to deflect gunshots with his bracers. Shang-Chi is also highly trained in the arts of concentration and meditation, and is an expert in various hand weapons including swords, staves, kali sticks, nunchaku, and shuriken.
Due to his martial arts prowess, Shang-Chi is a highly sought out teacher and has mentored many characters in kung fu and hand-to-hand combat. Some of
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Shang-Chi's most prominent students and sparring partners have included Captain America, Spider-Man, Wolverine, and Domino. Another testament to his skill as an instructor was during the "War of the Realms" where he was able to train a group of novices in a short amount of time, to the point where his proteges were able to easily fend off an army of powerful Fire Demons using the techniques he taught.
He is also very in tune with the chi emitted by all living beings, to the point where he was able to detect a psionically-masked Jean Grey by sensing her energy.
During his time with the Avengers, Shang-Chi was given special equipment by Tony Stark, including a pair of bracelets that allowed
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him to focus his chi in ways that increased his strength and a pair of repulsor-powered nunchaku.
Following exposure to the cosmic radiation from the Incursions, Shang-Chi was able to create an unlimited number of duplicates of himself.
# Other versions.
## Battleworld.
In the Battleworld, Shang-Chi fights against and eventually overthrows his father, Zheng Zu, the emperor of K'un-L'un and the Master of the Ten Rings.
## "House of M".
Shang-Chi never realizes his father's evil doings before his death at Magneto's hands. This causes him to become consumed with a desire for vengeance. In this reality, Shang-Chi is the head of the Dragons criminal organization, alongside Colleen Wing, Swordsman,
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Mantis, Zaran and Machete. The Dragons later resolved their rivalry against Luke Cage's gang, but were eventually captured in a trap created by both the Kingpin's assassins and Thunderbird's agents. The Dragons and the Wolfpack were freed by Luke Cage, in which Shang-Chi's gang join the Avengers in their battle against the Brotherhood.
## "Marvel Apes".
In this simian version of the Marvel Universe, Shang-Chi and his father work as a subversive organization, trying to get the local sentients to work in peace and not in animalistic domination. The Avengers (Ape-vengers) murder him for this 'weak-minded' sentiment.
## "Marvel Zombies".
In the Marvel Zombies continuity, Shang-Chi is turned
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into a zombie during a multi-hero effort to rescue surviving civilians. In a mid-Manhattan battle, detailed in "Ultimate Fantastic Four" #23, he and dozens of other zombie-heroes attempt to consume the last batch of humans. These humans are defended by that universe's Magneto and the Ultimate Fantastic Four. During a successful rescue attempt, Thing sends Shang-Chi flying through the air with one punch. Shang-Chi is then seen attacking Magneto once again, but he is cut in half by the Master of Magnetism. A different Shang-Chi appears in "Marvel Zombies Return" in an alternate universe where he is unaffected by the zombie outbreak. The zombie Wolverine finds him in an underground fight club,
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engaging with other infamous martial artists. The flesh-hungry mutant slashes him to death.
## "Ultimate Marvel".
In the Ultimate Marvel universe, Shang-Chi first appeared in "Ultimate Marvel Team-Up" #15. He is the son of an international crime lord. Trained from birth to become a living weapon, he became the world's greatest martial artist. A noble spirit, he eventually came to renounce his father's empire. Seeking to get away from his father's reach, he emigrated to New York where he worked as a floor sweeper at Wu's Fish Market in Chinatown. Feeling that the denizens of New York's Chinatown needed someone to protect them, he and his friend Danny Rand were drawn into the gang war between
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the Kingpin and Hammerhead after the latter targeted him to win over the Chinatown gangs to his cause. The conflict climaxed when Shang-Chi, Danny Rand, Spider-Man, Black Cat, Moon Knight and Elektra ambushed Hammerhead's penthouse, where a battle royale ensued. It ended with an unconscious Elektra, Hammerhead and Moon Knight. The gang members were then arrested by the police.
The martial arts warrior disguised himself as a costumed criminal in order to take down the Kingpin. The Kingpin discovered his plan and threatened to kill the hero, but he was rescued by Daredevil, who then recruited him as a part of his team to take down the Kingpin. After the Kingpin's identity is leaked to the New
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York Police Department, Shang-Chi and the team disbanded and went their separate ways.
## Earth-13584.
In A.I.M.'s pocket dimension of Earth-13584, Shang-Chi appears as a member of Spider-Man's gang.
# In other media.
## Film.
- According to Margaret Loesch, former President and CEO of Marvel Productions, in the 1980s Stan Lee considered Brandon Lee for the role of Shang-Chi and met with the actor and his mother Linda Lee to discuss a potential movie or television series starring the character.
- In 2006, Shang-Chi was chosen as one of the many properties in Marvel Studios' new film deal with Paramount Pictures, along with Captain America, Nick Fury, Doctor Strange, Hawkeye, Power Pack,
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Black Panther and Cloak and Dagger. In December 2018, Marvel Studios hired David Callaham to write the screenplay for a Shang-Chi film set in the Marvel Cinematic Universe. In March 2019, Destin Daniel Cretton was hired to direct. Guntis Sics, the sound mixer on "", revealed in an interview that filming will take place in Australia. At San Diego Comic-Con 2019, Simu Liu was announced to portray the character in the film "Shang-Chi and the Legend of the Ten Rings", set for a February 2021 release.
## Video games.
- Shang-Chi appears as an unlockable playable character in "Marvel Future Fight".
# Collected editions.
- "Shang-Chi: Master of Kung Fu" (collects "Shang-Chi: Master of Kung Fu"
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#1-6), 144 pages, May 2003,
- "Deadly Hands of Kung Fu: Out of the Past" (collects "Deadly Hands of Kung Fu" vol. 2 #1-4 and "The Deadly Hands of Kung Fu" vol. 1 #1, 32-33), 160 pages, November 4, 2014,
- "Master of Kung Fu: Battleworld" (collects "Master of Kung Fu" vol. 2 #1-4 and "Ronin" #2), 112 pages, January 2016,
- "Shang-Chi: Master of Kung Fu Omnibus"
- Vol. 1 collects "Special Marvel Edition" #15-16, "Master of Kung Fu" vol. 1 #17-37, "Giant-Size Master of Kung Fu" #1-4, "Giant-Size Spider-Man" #2 and material from "Iron Man Annual" vol. 1 #4, 696 pages, June 14, 2016,
- Vol. 2 collects "Master of Kung Fu" vol. 1 #38-70 and "Master of Kung Fu Annual" #1, 664 pages, September 20,
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2016,
- Vol. 3 collects "Master of Kung Fu" vol. 1 #71-101 and "What If?" #16, 696 pages, March 14, 2017,
- Vol. 4 collects "Master of Kung Fu" vol. 1 #102-125, "Marvel Comics Presents" vol. 1 #1-8 and "Master of Kung Fu: Bleeding Black" #1, 748 pages, October 17, 2017,
- "Deadly Hands of Kung Fu Omnibus"
- Vol. 1 collects "The Deadly Hands of Kung Fu" vol. 1 #1-18, "The Deadly Hands of Kung Fu Special Album Edition" and "The Deadliest Heroes of Kung Fu", 1,152 pages, November 15, 2016,
- Vol. 2 collects "The Deadly Hands of Kung Fu" vol. 1 #19-33 and material from "Bizarre Adventures" #25, 1,000 pages, June 20, 2017
# External links.
- Shang-Chi, Master of Kung Fu at Don Markstein's
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and "What If?" #16, 696 pages, March 14, 2017,
- Vol. 4 collects "Master of Kung Fu" vol. 1 #102-125, "Marvel Comics Presents" vol. 1 #1-8 and "Master of Kung Fu: Bleeding Black" #1, 748 pages, October 17, 2017,
- "Deadly Hands of Kung Fu Omnibus"
- Vol. 1 collects "The Deadly Hands of Kung Fu" vol. 1 #1-18, "The Deadly Hands of Kung Fu Special Album Edition" and "The Deadliest Heroes of Kung Fu", 1,152 pages, November 15, 2016,
- Vol. 2 collects "The Deadly Hands of Kung Fu" vol. 1 #19-33 and material from "Bizarre Adventures" #25, 1,000 pages, June 20, 2017
# External links.
- Shang-Chi, Master of Kung Fu at Don Markstein's Toonopedia. Archived from the original on February 15, 2016
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Marv Albert
Marv Albert
Marv Albert (born Marvin Philip Aufrichtig; June 12, 1941) is an American sportscaster. Honored for his work as a member of the Basketball Hall of Fame, he is commonly referred to as "the voice of basketball". From 1967 to 2004, he was also known as "the voice of the New York Knicks". Albert currently works for Turner Sports, serving as lead announcer for NBA games on TNT.
In addition to calling both professional and college basketball, he has experience announcing other sports such as American football, ice hockey, horse racing, boxing, and tennis. Albert has called the play-by-play of eight Super Bowls, NBA Finals, and seven Stanley Cup Finals. He has also called the Wimbledon
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Marv Albert
Tennis Championships for TNT with Jim Courier and Mary Carillo. He also worked as a co-host and reporter for two World Series (1986 and 1988)
# Early life.
Albert was born to a Jewish family in Brooklyn, where he went to Abraham Lincoln High School. While Albert grew up, members of his family owned a grocery store on Brighton Beach Avenue between 3rd and 4th streets known as Aufrichtig's. He then attended Syracuse University's Newhouse School of Public Communications from 1960 through 1963. In 1962, he served as the voice of the AAA Syracuse Chiefs. He then graduated from New York University in 1965.
# Broadcasting career.
## National Basketball Association.
### New York Knicks (MSG).
Marv
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did his first Knicks game on January 27, 1963 on WCBS Radio. He filled in for his mentor, Marty Glickman, who was away in Europe. The game was against the Celtics at the Boston Garden. For 37 years beginning in 1967, Albert was the voice of the New York Knicks on radio and television (getting his start by being a ball boy for the Knicks before getting his first break on New York radio by sportscaster Marty Glickman) before being let go by James L. Dolan, the chairman of the MSG Network and Cablevision, after Albert criticized the Knicks' poor play on-air in 2004. It was said that Marv's high salary was also a factor. His son Kenny Albert has been a part-time play-by-play announcer for the Knicks
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since 2009, whenever the older Albert's successor Mike Breen (whom he later followed on the "NBA on NBC" broadcasts and now works on ESPN and ABC aside from his role at MSG) is unavailable.
For a brief period before he resumed his normal broadcasting duties following his sexual assault arrest (see below), Albert anchored MSG's former nightly sports news report, "MSG SportsDesk".
### NBC Sports.
Marv Albert was the lead play-by-play broadcaster for the "NBA on NBC" for most of its run from 1990 to 2002, calling every NBA Finals during that timeframe except for 1998, 1999, and 2000. During this time, Bob Costas had taken over the lead job and called the Finals after Marv's arrest for sexual
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Marv Albert
assault had brought him national disgrace. Marv resumed his previous position for the 2000–2001 season and called Game 4 of the 2002 NBA Finals which was the final NBA telecast on NBC. During his time on NBC, Albert continued as lead play-by-play man for the New York Knicks on local MSG Network telecasts and began calling national games for TNT in 1999 as well. When he regained the lead broadcaster position on NBC, he continued to call play-by-play for both networks until the end of NBC's coverage in 2002.
### TNT.
Albert continues to be the lead play-by-play announcer for National Basketball Association games on TNT, a position he assumed in 1999. Indeed, TNT has become his primary commitment
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Marv Albert
ever since his longtime employer NBC lost the NBA broadcasting rights in 2002, and may have played a role in his departure from the Knicks' broadcast booth. The Knicks reportedly wanted Albert to accept a salary commensurate with his reduced Knicks schedule, but also weren't happy about Albert making what Knicks management felt were overly critical comments about their team in spite of their losing record.
In basketball, his most famous call is his simple "Yes!" for a basket, rendered in many variations of volume and length depending on the situation; and a catchphrase that he began using in his youth when playing pickup games with friends.
On April 17, 2002, shortly after calling a game between
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Marv Albert
the Indiana Pacers and Philadelphia 76ers on TNT, both Albert and color analyst Mike Fratello were injured in a limo accident in Trenton, New Jersey. Albert sustained facial lacerations, a concussion, and a sprained ankle. The 2002 NBA Playoffs were set to begin two days later, with Albert scheduled to call multiple games that week. Bob Costas filled in those games and Albert returned to call Game 1 of the Western Conference Semifinals between the Dallas Mavericks and Sacramento Kings.
In 2018, Sports Broadcast Journal speculated that Albert might be the first network play-by-play broadcaster to continue into his 80s, Will Marv Albert be the first network play-by-play announcer to call games
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into his 80s
### New Jersey Nets (YES).
In 2005, Albert officially became the lead play-by-play man for the New Jersey Nets franchise and started calling their games on the YES Network, often teaming with Brooklyn native and NBA veteran, Mark Jackson. With that, the Nets employed all three Albert brothers during the franchise's history; Al started his broadcast career with the Nets during their ABA days, while Steve called Nets games during the late 1970s and 1980s. Beginning with the 2008–09 season, Albert was also paired with his TNT broadcast colleague Mike Fratello on the YES Network. However, with the Nets' struggles in the 2009–10 season, Nets management relegated Albert to secondary
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Marv Albert
play-by-play, to avoid a similar incident while Albert was with the Knicks. Since then Ian Eagle has taken over the broadcasts. In 2011, Albert left the YES Network to join CBS Sports for NFL and NCAA tournament coverage.
### Other basketball-related duties.
Albert hosts a basketball-focused interview show on NBA TV, which also airs later on YES.
Since 2003, Albert has also been providing the play-by-play voice on the "NBA Live" video-game series on EA Sports, a role he fulfilled until "NBA Live 10".
From 2011 to 2015, Albert announced NCAA Men's Division I Basketball Championship tournament games, the result of longtime tournament broadcaster CBS handing off some of its coverage to Turner
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Sports.
In February 2016, Albert and Turner Sports announced that he would no longer call NCAA Tournament basketball games, stating that calling four games in one day during the first round, and a total of six matches in three days during the first two rounds, was too much for his 74-year-old voice to handle. Albert said that he "felt it was the wiser move to go primarily NBA at this stage".
## Outside basketball.
### New York Rangers.
In addition to the Knicks, Albert had a lengthy tenure (beginning in 1965) calling the games of another Madison Square Garden tenant, the New York Rangers. He handled the radio call of the Rangers' Stanley Cup–clinching victory in 1994.
He also famously coined
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the nickname "Red Light" for radio analyst Sal Messina, a former Rangers goaltender. His signature play-by-play phrase was "kick save and a beauty."
Over his years as the Rangers broadcaster, Albert missed a large number of games for other commitments. Many other broadcasters filled in, including several who later served long stints for other NHL teams, including Howie Rose, Mike Emrick and John Kelly, as well as brothers Al and Steve. It was Albert's absence from Game 7 of the Rangers–Devils Conference Championship game that led to Rose's famed "Matteau, Matteau, Matteau" call.
Albert left the Rangers after the 1994–95 season at the same time Rose took the job as play-by-play announcer of
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the New York Islanders. Albert's son, Kenny, replaced him, and has been the radio voice of the Rangers ever since. Kenny also calls NHL and Olympic ice hockey for NBC Sports, while also serving as the national radio voice of the Stanley Cup Finals since 2016.
### New York Giants.
From 1973 to 1976, Albert called radio broadcasts of New York Giants football games, succeeding Marty Glickman after the latter's defection to the New York Jets.
### "Monday Night Football".
Albert was also the lead play-by-play voice of the Westwood One radio network's NFL coverage from 2002 to 2009 seasons, calling "Monday Night Football" as well as numerous playoff games and every Super Bowl from 2003 to 2010.
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On June 4, 2010, it was announced that Albert was leaving his "NFL on Westwood One" duties. He was succeeded on the broadcasts by Kevin Harlan.
### "NFL on CBS".
On June 6, 2011, it was announced that Albert was joining CBS Sports to call play-by-play for "The NFL on CBS". Albert was usually teamed with Rich Gannon on broadcasts.
On May 29, 2014, Albert stepped down from calling "The NFL on CBS" to focus more on his basketball duties for TNT and CBS.
### Other network duties.
Other NBC Sports duties that Albert held were play-by-play announcing for the NFL (by 1983, Albert was the #2 play-by-play man behind Dick Enberg, usually alternating the secondary NFL role year to year with Don Criqui),
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Marv Albert
college basketball (teaming with Bucky Waters on Big East/ECAC games), horse racing, boxing (often working with Ferdie Pacheco and subsequently, Sugar Ray Leonard when NBC relaunched boxing under the "Premier Boxing Champions" umbrella), NHL All-Star Games (Albert called the NHL All-Star Game with John Davidson on NBC from 1990-1994), and Major League Baseball, as well as hosting baseball (including NBC's coverage of the 1986 and 1988 World Series alongside Bob Costas). He also spent 13 years as the sports director of the network's flagship station, WNBC-TV in New York.
Albert also called regular-season and playoff NHL games for the syndicated NHL Network in the 1976–77 season, and from 2000
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to 2002 he helped call TNT's coverage of the Wimbledon Championships tennis tournament.
## Popularity.
Albert made 126 guest appearances on David Letterman's late night talk shows for NBC and CBS. Each time Albert appeared, he brought with him a group of clips featuring sports bloopers and outstanding plays, which he narrated and dubbed the "Albert Achievement Awards". The music accompanying the bloopers was "12th Street Rag".
Albert was placed as number 14 on David J. Halberstam's list of Top 50 All Time Network Television Sports Announcers on Yahoo! Sports.
In 1992, he appeared as himself on Roger Waters' rock album "Amused to Death", giving a play-by-play account of the destruction of
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Marv Albert
an oil rig on the song "Perfect Sense, Part II".
An "Albert Achievement Awards" video was released in 1993. It featured cameos by Mike Fratello, Ahmad Rashād, Charles Barkley, David Letterman, O.J. Simpson, Bob Costas, and Tom Brokaw.
Albert became the first guest commentator in MTV's "Celebrity Deathmatch" cartoon series. He appeared in the 1998 pilot episode before being replaced with Stacey Cornbred.
Albert was briefly mentioned in the 2006 film "Grandma's Boy".
Albert's voice is imitated in Futurama, in the Season 3 episode "Time Keeps On Slippin'" in 2001.
Albert also appeared as a special guest on "The Simpsons", in the Season 20 episode "The Burns and the Bees" in 2008.
Albert’s
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voice is imitated in Pinky and the Brain, in the season 2, episode "Hoop Schemes" in 1997.
Albert's voice is imitated in the popular video game "NBA Jam". The announcer was modeled on Albert although there is no mention of Albert in the game and was actually voiced by Tim Kitzrow.
Albert did play-by-play commentary in the video games "NFL Quarterback Club '98" and "NBA Live".
In the 1999 episode "Tube Steaks" of the CBS sitcom "The King of Queens", Doug and his friends watch a Knicks-game with Albert's voice commentary.
He authored (with Rick Reilly) an autobiography, "I'd Love to But I Have a Game", in 1993.
Albert appeared in a short scene in the 2015 comedy film "Trainwreck".
Albert
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did the commentary, along with Mike Fratello and Steve Kerr, on NBA Live video games made by EA Sports from 2003 to 2009.
## Honors and awards.
- Cable ACE Award – six times.
- Curt Gowdy Media Award – awarded by the Naismith Memorial Basketball Hall of Fame, 1994.
- American Sportscasters Association Sportscaster of the Year (Play-by-Play) – 1996. Other honorees included Sportscaster of the Year (Studio Host) Chris Berman, Hall of Fame inductee Jack Whitaker, Sports Legend Joe Frazier and Honorary Sportscaster Dr. Henry Kissinger.
- Emmy Award – for national sports: five times; for New York: three times.
- Nassau County Sports Hall of Fame – inducted in 2006.
- National Jewish Museum
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Marv Albert
Sports Hall of Fame – inducted in 1992.
- New York State Sportscaster of the Year – twenty times.
- Noted in Roger Waters' album, "Amused to Death".
- National Sportscasters and Sportswriters Association Hall of Fame – inducted in 2014.
# Family.
Albert's son, Kenny, is also a sports commentator, who calls baseball and football for Fox, New York Rangers games on the radio, and has been one of NBC's commentators for ice hockey at the Winter Olympics, as well as NBC's NHL coverage. His daughter, Denise, is a reporter for NBA TV.
Marv has two younger brothers who also are announcers. Steve Albert was the Phoenix Suns play-by-play announcer before his retirement following the 2016-17 season,
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and has also called play-by-play for several other teams, including the New Orleans Hornets, New Jersey Nets, New York Islanders, New York Mets, and Golden State Warriors. Steve is best known for his work on "Showtime Championship Boxing", notably the Holyfield–Tyson bouts. Al Albert was the former play-by-play announcer for the New York Nets (ABA), "USA Tuesday Night Fights", the Indiana Pacers and the Denver Nuggets. Al also called national NBA games on the USA Network during its brief tenure in the early 1980s.
# Sexual assault.
Albert became embroiled in a sex scandal in 1997. A 42-year-old woman named Vanessa Perhach accused Albert of throwing her on a bed, biting her, and forcing her
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to perform oral sex after a February 12, 1997 argument in his Pentagon City hotel room. DNA testing linked Albert to genetic material taken from the bite marks and from semen in Perhach's underwear. During the trial, testimony was presented from another woman, Patricia Masden, who told the jury that Albert had bitten her on two different occasions in 1993 and 1994 in Miami and Dallas hotels, which she viewed as unwanted sexual advances. Masden claimed that in Dallas, Albert called her to his hotel room to help him send a fax, only for her to find him wearing "white panties and garter belt". Albert maintained that Perhach had requested that he bite her and denied her accusation that he'd asked
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her to bring another man into their sexual affair. He described the recorded conversation of hers with the police on the night of the incident as "an Academy Award performance". After tests proved that the bite marks were his, he pleaded guilty to misdemeanor assault and battery charges, while the sodomy charge was dropped. Albert was given a 12-month suspended sentence.
## Ousted from NBC.
Consequently, NBC – for which Albert worked for over 20 years – fired him shortly before the 1997–98 NBA season began on "The NBA on NBC". Bob Costas took over for Albert on the basketball side in the 1997–98 season before stepping down after the 2000 NBA Finals for Albert's return. In addition, Tom Hammond
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spelled his football duties. It is also revealed on a "Simpsons" DVD commentary that he was to appear in the episode "Bart Star" but, due to the scandal, was replaced by Roy Firestone.
## Return to NBC.
NBC brought Albert back less than two years later, and he was the network's main play-by-play man for the 2000–01 and 2001–02 NBA seasons, including the Finals (working with Doug Collins and later Bill Walton and Steve Jones respectively). NBC lost the rights to the NBA to ABC following the 2001–02 season.
# Broadcasting partners.
- John Andariese
- Butch Beard
- Bill Chadwick
- Chip Cipolla
- Doug Collins
- Cris Collinsworth
- John Davidson
- Boomer Esiason
- Mike Fratello
- Walt
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001–02 NBA seasons, including the Finals (working with Doug Collins and later Bill Walton and Steve Jones respectively). NBC lost the rights to the NBA to ABC following the 2001–02 season.
# Broadcasting partners.
- John Andariese
- Butch Beard
- Bill Chadwick
- Chip Cipolla
- Doug Collins
- Cris Collinsworth
- John Davidson
- Boomer Esiason
- Mike Fratello
- Walt Frazier
- Rich Gannon
- Richie Guerin
- Matt Guokas
- Sam Huff
- Magic Johnson
- Steve "Snapper" Jones
- Steve Kerr
- Dick Lynch
- Paul Maguire
- Sal Messina
- Reggie Miller
- Earl Monroe
- Bill Parcells
- Cal Ramsey
- Bob Trumpy
- Jeff Van Gundy
- Bill Walton
- Bucky Waters
- Chris Webber
- Sam Wyche
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MIPS
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https://en.wikipedia.org/w/index.php?title=MIPS
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MIPS
MIPS
MIPS may refer to:
# Technology.
- Million instructions per second, a measure of a computer's central processing unit performance
- MIPS architecture, a RISC instruction set architecture
- Multiband Imaging Photometer for Spitzer, an instrument on the Spitzer Space Telescope
- Multi-directional Impact Protection System, a helmet safety technology
- Stanford MIPS, a research project
- MIPS-X, a follow-on project to the Stanford MIPS
# Organizations.
- Maharana Institute of Professional Studies, an institution in Kanpur, Uttar Pradesh, India
- Mansehra International Public School and College in Mansehra, Pakistan
- MIPS Technologies, formerly MIPS Computer Systems, the developer
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tems, the developer of the MIPS architecture
- Monash Institute of Pharmaceutical Science (MIPS) in Parkville, Victoria
- Munich Information Center for Protein Sequences, a genomics research center in Germany
# Other.
- Material input per unit of service, an economic efficiency indicator
- Menards Infiniti Pro Series, a former name of an Indy Pro Series automobile race
- Monthly income preferred stock, a financial instrument
- MIPS, a rabbit in "Super Mario 64"
- Minimum Ionizing Particles, a term widely used in experimental particle physics
- Merit-based Incentive Payment System, a part of the Medicare Access and CHIP Reauthorization Act of 2015
# See also.
- MIP (disambiguation)
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Metallocene
|
https://en.wikipedia.org/w/index.php?title=Metallocene
|
Metallocene
Metallocene
A metallocene is a compound typically consisting of two cyclopentadienyl anions (, abbreviated Cp) bound to a metal center (M) in the oxidation state II, with the resulting general formula (CH)M. Closely related to the metallocenes are the metallocene derivatives, e.g. titanocene dichloride, vanadocene dichloride. Certain metallocenes and their derivatives exhibit catalytic properties, although metallocenes are rarely used industrially. Cationic group 4 metallocene derivatives related to [CpZrCH] catalyze olefin polymerization.
Some metallocenes consist of metal plus two cyclooctatetraenide anions (, abbreviated cot), namely the lanthanocenes and the actinocenes (uranocene and others).
Metallocenes
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are a subset of a broader class of compounds called sandwich compounds .
In the structure shown at right, the two pentagons are the cyclopentadienyl anions with circles inside them indicating they are aromatically stabilized. Here they are shown in a staggered conformation.
# History.
The first metallocene to be classified was ferrocene, and was discovered simultaneously in 1951 by Kealy and Pauson, and Miller et al. Kealy and Pauson were attempting to synthesize fulvalene through the oxidation of a cyclopentadienyl salt with anhydrous FeCl but obtained instead the substance CHFe At the same time, Miller "et al" reported the same iron product from a reaction of cyclopentadiene with iron in
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the presence of aluminum, potassium, or molybdenum oxides. The structure of "CHFe" was determined by Wilkinson et al. and by Fischer et al. These two were awarded the Nobel Prize in Chemistry in 1973 for their work on sandwich compounds, including the structural determination of ferrocene. They determined that the carbon atoms of the cyclopentadienyl (Cp) ligand contributed equally to the bonding and that bonding occurred due to the metal d-orbitals and the π-electrons in the p-orbitals of the Cp ligands. This complex is now known as ferrocene, and the group of transition metal dicyclopentadienyl compounds is known as metallocenes. Metallocenes have the general formula [("η"-CH)M]. Fischer et
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al. first prepared the ferrocene derivatives involving Co and Ni. Often derived from substituted derivatives of cyclopentadienide, metallocenes of many elements have been prepared.
One of the very earliest commercial manufacturers of metallocenes was Arapahoe Chemicals in Boulder, Colorado.
# Definition.
The general name metallocene is derived from ferrocene, (CH)Fe or CpFe, systematically named bis("η"-cyclopentadienyl)iron(II). According to the IUPAC definition, a metallocene contains a transition metal and two cyclopentadienyl ligands coordinated in a sandwich structure, i.e., the two cyclopentadienyl anions are on parallel planes with equal bond lengths and strengths. Using the nomenclature
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of "hapticity", the equivalent bonding of all 5 carbon atoms of a cyclopentadienyl ring is denoted as "η", pronounced "pentahapto". There are exceptions, such as uranocene, which has two cyclooctatetraene rings sandwiching a uranium atom.
In metallocene names, the prefix before the "-ocene" ending indicates what metallic element is between the Cp groups. For example, in ferrocene, iron(II), ferrous iron is present.
In contrast to the more strict definition proposed by IUPAC, which requires a d-block metal and a sandwich structure, the term metallocene and thus the denotation "-ocene", is applied in the chemical literature also to non-transition metal compounds, such as barocene (CpBa), or
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structures where the aromatic rings are not parallel, such as found in manganocene or titanocene dichloride (CpTiCl).
Some metallocene complexes of actinides have been reported where there are three cyclopendadienyl ligands for a monometallic complex, all three of them bound η.
# Classification.
There are many ("η"-CH)–metal complexes and they can be classified by the following formulas:
Metallocene complexes can also be classified by type:
- 1. Parallel
- 2. Multi-decker
- 3. Half-sandwich compound
- 4. Bent metallocene or tilted
- 5. More than two Cp ligands
# Synthesis.
Three main routes are normally employed in the formation of these types of compounds:
## Using a metal salt
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and cyclopentadienyl reagents.
Sodium cyclopentadienide (NaCp) is the preferred reagent for these types of reactions. It is most easily obtained by the reaction of molten sodium and dicyclopentadiene. Traditionally, the starting point is the cracking of dicyclopentadienyl, the dimer of cyclopentadiene. Cyclopentadiene is deprotonated by strong bases or alkali metals.
NaCp acts as a reducing agent and a ligand in this reaction.
## Using a metal and cyclopentadiene.
This technique provides using metal atoms in the gas phase rather than the solid metal. The highly reactive atoms or molecules are generated at a high temperature under vacuum and brought together with chosen reactants on a cold
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surface.
## Using cyclopentadienyl reagents.
A variety of reagents have been developed that transfer Cp to metals. Once popular was thallium cyclopentadienide. It reacts with metal halides to give thallium chloride, which is poorly soluble, and the cyclopentadienyl complex. Trialkyltin derivatives of Cp have also been used.
Many other methods have been developed. Chromocene can be prepared from chromium hexacarbonyl by direct reaction with cyclopentadiene in the presence of diethylamine; in this case, the formal deprotonation of the cyclopentadiene is followed by reduction of the resulting protons to hydrogen gas, facilitating the oxidation of the metal centre.
Metallocenes generally have
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high thermal stability. Ferrocene can be sublimed in air at over 100 °C with no decomposition; metallocenes are generally purified in the laboratory by vacuum sublimation. Industrially, sublimation is not practical so metallocenes are isolated by crystallization or produced as part of a hydrocarbon solution. For Group IV metallocenes, donor solvents like ether or THF are distinctly undesirable for polyolefin catalysis. Charge-neutral metallocenes are soluble in common organic solvents. Alkyl substitution on the metallocene increases the solubility in hydrocarbon solvents.
# Structure.
A structural trend for the series MCp involves the variation of the M-C bonds, which elongate as the valence
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electron count deviates from 18.
In metallocenes of the type (CR)M, the cyclopentadienyl rings rotate with very low barriers. Single crystal X-ray diffraction studies reveal both eclipsed or staggered rotamers. For non-substituted metallocenes the energy difference between the staggered and eclipsed conformations is only a few kJ/mol. Crystals of ferrocene and osmocene exhibit eclipsed conformations at low temperatures, whereas in the related bis(pentamethylcyclopentadienyl) complexes the rings usually crystallize in a staggered conformation, apparently to minimize steric hindrance between the methyl groups.
# Spectroscopic properties.
## Vibrational (infrared and Raman) spectroscopy of metallocenes.
Infrared
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and Raman spectroscopies have proved to be important in the analysis of cyclic polyenyl metal sandwich species, with particular use in elucidating covalent or ionic M–ring bonds and distinguishing between central and coordinated rings. Some typical spectral bands and assignments of iron group metallocenes are shown in the following table:
## NMR (H and C) spectroscopy of metallocenes.
Nuclear magnetic resonance (NMR) is the most applied tool in the study of metal sandwich compounds and organometallic species, giving information on nuclear structures in solution, as liquids, gases, and in the solid state. H NMR chemical shifts for diamagnetic organotransition-metal compounds is usually observed
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between 25 and 40 ppm, but this range is much more narrow for diamagnetic metallocene complexes, with chemical shifts usually observed between 3 and 7 ppm.
## Mass spectrometry of metallocenes.
Mass spectrometry of metallocene complexes has been very well studied and the effect of the metal on the fragmentation of the organic moiety has received considerable attention and the identification of metal-containing fragments is often facilitated by the isotope distribution of the metal. The three major fragments observed in mass spectrometry are the molecular ion peak, [CHM], and fragment ions, [CHM] and M.
# Derivatives.
After the discovery of ferrocene, the synthesis and characterization of
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derivatives of metallocene and other sandwich compounds attracted researchers’ interests.
## Metallocenophanes.
Metallocenophanes feature linking of the cyclopentadienyl or polyarenyl rings by the introduction of one or more heteroannular bridges. Some of these compounds undergo thermal ring-opening polymerizations (ROP) to give soluble high molecular weight polymers with transition metals in the polymer backbone. Ansa-metallocenes are derivatives of metallocenes with an intramolecular bridge between the two cyclopentadienyl rings.
## Polynuclear and heterobimetallic metallocenes.
- Ferrocene derivatives: biferrocenophanes have been studied for their mixed valence properties. Upon one-electron
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oxidation of a compound with two or more equivalent ferrocene moieties, the electron vacancy could be localized on one ferrocene unit or completely delocalized.
- Ruthenocene derivatives: in the solid state biruthenocene is disordered and adopts the transoid conformation with the mutual orientation of Cp rings depending on the intermolecular interactions.
- Vanadocene and rhodocene derivatives: vanadocene complexes have been used as starting materials for the synthesis of heterobimetallic complexes. The 18 valence electron ions [CpRh] are very stable, unlike the neutral monomers CpRh which dimerize immediately at room temperature and they have been observed in matrix isolation.
## Multi-decker
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sandwich compounds.
Triple-decker complexes are composed of three Cp anions and two metal cations in alternating order. The first triple-decker sandwich complex, [NiCp], was reported in 1972. Many examples have been reported subsequently, often with boron-containing rings.
## Metallocenium cations.
The most famous example is ferrocenium, [Fe(CH)], the blue iron(III) complex derived from oxidation of orange iron(II) ferrocene (few metallocene anions are known).
# Applications.
Many derivatives of early metal metallocenes are active catalysts for olefin polymerization. Unlike traditional and still dominant heterogeneous Ziegler–Natta catalysts, metallocene catalysts are homogeneous. Early
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still dominant heterogeneous Ziegler–Natta catalysts, metallocene catalysts are homogeneous. Early metal metallocene derivatives, e.g. Tebbe's reagent, Petasis reagent, and Schwartz's reagent are useful in specialized organic synthetic operations.
## Potential applications.
The ferrocene/ferrocenium biosensor has been discussed for determining the levels of glucose in a sample electrochemically through a series of connected redox cycles.
Metallocene dihalides [CpMX] (M = Ti, Mo, Nb) exhibit anti-tumor properties, although none have proceeded far in clinical trials.
Metallocenes may be useful for isotope separation.
# See also.
- Jemmis "mno" rules
- Actinocenes
- f-block metallocene
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Maze
A maze is a path or collection of paths, typically from an entrance to a goal. The word is used to refer both to branching tour puzzles through which the solver must find a route, and to simpler non-branching ("unicursal") patterns that lead unambiguously through a convoluted layout to a goal. (The term "labyrinth" is generally synonymous with "maze", but can also connote specifically a unicursal pattern.) The pathways and walls in a maze are typically fixed, but puzzles in which the walls and paths can change during the game are also categorised as mazes or tour puzzles.
# Maze construction.
Mazes have been built with walls and rooms, with hedges, turf, corn stalks, straw bales, books,
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paving stones of contrasting colors or designs, and brick, or in fields of crops such as corn or, indeed, maize. Maize mazes can be very large; they are usually only kept for one growing season, so they can be different every year, and are promoted as seasonal tourist attractions. Indoors, mirror mazes are another form of maze, in which many of the apparent pathways are imaginary routes seen through multiple reflections in mirrors. Another type of maze consists of a set of rooms linked by doors (so a passageway is just another room in this definition). Players enter at one spot, and exit at another, or the idea may be to reach a certain spot in the maze. Mazes can also be printed or drawn on
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paper to be followed by a pencil or fingertip. Mazes can be built with snow.
# Generating mazes.
Maze generation is the act of designing the layout of passages and walls within a maze. There are many different approaches to generating mazes, with various maze generation algorithms for building them, either by hand or automatically by computer.
There are two main mechanisms used to generate mazes. In "carving passages", one marks out the network of available routes. In building a maze by "adding walls", one lays out a set of obstructions within an open area. Most mazes drawn on paper are done by drawing the walls, with the spaces in between the markings composing the passages.
# Solving mazes.
Maze
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solving is the act of finding a route through the maze from the start to finish. Some maze solving methods are designed to be used inside the maze by a traveler with no prior knowledge of the maze, whereas others are designed to be used by a person or computer program that can see the whole maze at once.
The mathematician Leonhard Euler was one of the first to analyze plane mazes mathematically, and in doing so made the first significant contributions to the branch of mathematics known as topology.
Mazes containing no loops are known as "standard", or "perfect" mazes, and are equivalent to a "tree" in graph theory. Thus many maze solving algorithms are closely related to graph theory. Intuitively,
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if one pulled and stretched out the paths in the maze in the proper way, the result could be made to resemble a tree.
# Mazes in psychology experiments.
Mazes are often used in psychology experiments to study spatial navigation and learning. Such experiments typically use rats or mice. Examples are:
- Barnes maze
- Morris water maze
- Oasis maze
- Radial arm maze
- Elevated plus maze
- T-maze
# Other types of mazes.
- Ball-in-a-maze puzzles: Dexterity puzzles which involve navigating a ball through a maze or labyrinth.
- Block maze: A maze in which the player must complete or clear the maze pathway by positioning blocks. Blocks may slide into place or be added.
- Hamilton maze: A
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maze in which the goal is to find the unique Hamiltonian cycle.
- Linear or railroad maze: A maze in which the paths are laid out like a railroad with switches and crossovers. Solvers are constrained to moving only forward. Often, a railroad maze will have a single track for entrance and exit.
- Logic mazes: These are like standard mazes except they use rules other than "don't cross the lines" to restrict motion.
- Loops and traps maze: A maze that features one-way doors. The doors can lead to the correct path or create traps that divert you from the correct path and lead you to the starting point. The player may not return through a door through which he has entered, so dead ends may be
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created. The path is a series of loops interrupted by doors. Through the use of reciprocal doors, the correct path can intersect the incorrect path on a single plane. A graphical variant of this maze type is an arrow maze.
- Mazes in higher dimensions: It is possible for a maze to have three or more dimensions. A maze with bridges is three-dimensional, and some natural cave systems are three-dimensional mazes. The computer game "Descent" uses fully three-dimensional mazes. Any maze can be mapped into a higher dimension without changing its topology.
- Number maze: A maze in which numbers are used to determine jumps that form a pathway, allowing the maze to criss-cross itself many times.
-
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Picture maze: A standard maze that forms a picture when solved.
- Turf mazes and mizmazes: A pattern like a long rope folded up, without any junctions or crossings.
# Publications about mazes.
Numerous mazes of different kinds have been drawn, painted, published in books and periodicals, used in advertising, in software, and sold as art. In the 1970s there occurred a publishing "maze craze" in which numerous books, and some magazines, were commercially available in nationwide outlets and devoted exclusively to mazes of a complexity that was able to challenge adults as well as children (for whom simple maze puzzles have long been provided both before, during, and since the 1970s "craze").
Some
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of the best-selling books in the 1970s and early 1980s included those produced by Vladimir Koziakin, Rick and Glory Brightfield, Dave Phillips, Larry Evans, and Greg Bright. Koziakin's works were predominantly of the standard two-dimensional "trace a line between the walls" variety. The works of the Brightfields had a similar two-dimensional form but used a variety of graphics-oriented "path obscuring" techniques. Although the routing was comparable to or simpler than Koziakin's mazes, the Brightfields' mazes did not allow the various pathway options to be discerned easily by the roving eye as it glanced about.
Greg Bright's works went beyond the standard published forms of the time by including
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"weave" mazes in which illustrated pathways can cross over and under each other. Bright's works also offered examples of extremely complex patterns of routing and optical illusions for the solver to work through. What Bright termed "mutually accessible centers" ("The Great Maze Book", 1973) also called "braid" mazes, allowed a proliferation of paths flowing in spiral patterns from a central nexus and, rather than relying on "dead ends" to hinder progress, instead relied on an overabundance of pathway choices. Rather than have a single solution to the maze, Bright's routing often offered multiple equally valid routes from start to finish, with no loss of complexity or diminishment of solver difficulties
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because the result was that it became difficult for a solver to definitively "rule out" a particular pathway as unproductive. Some of Bright's innovative mazes had no "dead ends", although some clearly had looping sections (or "islands") that would cause careless explorers to keep looping back again and again to pathways they had already travelled.
The books of Larry Evans focused on 3-D structures, often with realistic perspective and architectural themes, and Bernard Myers ("Supermazes" No. 1) produced similar illustrations. Both Greg Bright ("The Hole Maze Book") and Dave Phillips ("The World's Most Difficult Maze") published maze books in which the sides of pages could be crossed over and
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in which holes could allow the pathways to cross from one page to another, and one side of a page to the other, thus enhancing the 3-D routing capacity of 2-D printed illustrations.
Adrian Fisher is both the most prolific contemporary author on mazes, and also one of the leading maze designers. His book "The Amazing Book of Mazes" (2006) contains examples and photographs of numerous methods of maze construction, several of which have been pioneered by Fisher; "The Art of the Maze" (Weidenfeld & Nicolson, 1990) contains a substantial history of the subject, whilst "Mazes and Labyrinths" (Shire Publications, 2004) is a useful introduction to the subject.
A recent book by Galen Wadzinski ("The
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Ultimate Maze Book") offers formalized rules for more recent innovations that involve single-directional pathways, 3-D simulating illustrations, "key" and "ordered stop" mazes in which items must be collected or visited in particular orders to add to the difficulties of routing (such restrictions on pathway traveling and re-use are important in a printed book in which the limited amount of space on a printed page would otherwise place clear limits on the number of choices and pathways that can be contained within a single maze). Although these innovations are not all entirely new with Wadzinski, the book marks a significant advancement in published maze puzzles, offering expansions on the traditional
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puzzles that seem to have been fully informed by various video game innovations and designs, and adds new levels of challenge and complexity in both the design and the goals offered to the puzzle-solver in a printed format.
# Mazes open to the public.
## Asia.
### Dubai.
- Gardens Shopping Mall, Dubai (world's largest indoor maze)
### Japan.
- Hikimi no Meiro, Kiso, Nagano, Japan
- Kyodai Meiro Palladium, Nikkō, Tochigi, Japan
- Sendai Hi-Land, Sendai, Miyagi, Japan
- Shirahama Energy Land, Shirahama, Wakayama, Japan
## Pacific.
### New Zealand.
- Amazing Maze n' Maize
- The Great Maze at Puzzling World
## Europe.
### Austria.
- Schönbrunn Palace, Vienna, has a large hedge maze
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