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- W1991340147 abstract "The thermal decomposition at 110° C of a 7-chloromethyl-7-phosphanorbornadiene PW(CO)5 complex generates the transient terminal phosphinidene complex (ClCH2PW(CO)5] which can be trapped by tolane to give (1-chloromethyl-2,3-diphenylphosphirene) pentacarbonyltungsten. In contrast, in the presence of CuCl at 60° C, the terminal phosphinidene complex rearranges to give (methylenechlorophosphine) pentacarbonyltungsten which has been characterized by 1H, 13C, and 31P NMR spectroscopy. The huge 1J(CP) coupling constant of 103.8 Hz establishes the presence of a PC double bond. This double bond reacts with HCl and α-enones to give the expected addition and [4 + 2] cycloaddition products. In the presence of AlCl3, a fast reaction takes place with ferrocene to give the corresponding methyl-ferrocenyl-chlorophosphine complex. La décomposition thermique à 110° C d'un complexe de chlorométhyl-7-phospha-7 norbornadiène engendre un complexe terminal de phosphinidène [ClCH2-PW(CO)5] que l'on peut piéger par du tolane pour obtenir le (chlorométhyl-1 diphényl-2,3 phosphirène)pentacarbonyltungstène. A 60° C en présence de CuCl, ce complexe de phosphinidène se réarrange rapidement pour donner le complexe de la méthylènechlorophosphine qui a été complètement caractérisé par spectroscopie RMN 1H, 13C et 31P. L'énorme constante de couplage 1J(CP) de 103.8 Hz démonstre la présence d'une double liaison PC. Cette double liaison réagit avec HCl et les α-énones pour donner les produits dáddition et de cycloaddition attendus. En présence de AlCl3, on observe une réaction rapide avec le ferrocène qui conduit au complexe de méthyl-ferrocényl-chlorophosphine." @default.
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- W1991340147 date "1988-10-01" @default.
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- W1991340147 title "Données complémentaires sur la synthèse, les proprietés spectroscopiques et la chimie du complexe [méthylènechlorophosphine]pentacarbonyltungstène" @default.
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- W1991340147 doi "https://doi.org/10.1016/0022-328x(88)80641-7" @default.
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