Donnees complementaires sur la synthese, les proprietes spectroscopiques et la chimie du complexe pentacarbonyltungstene

Article abstract of DOI:10.1016/0022-328X(88)80641-7

The thermal decomposition at 110 deg C of a 7-chloromethyl-7-phosphanorbornadiene PW(CO)5 complex generates the transient terminal phosphinidene complex which can be trapped by tolane to give (1-chloromethyl-2,3-diphenylphosphirene)pentacarbonyltungsten.In contrast, in the presence of CuCl at 60 deg C, the terminal phosphinidene complex rearranges to give (methylenechlorophosphine)pentacarbonyltungsten which has been characterized by 1H, 13C, and 31P NMR spectroscopy.The huge ¹J(C-P) coupling constant of 103.8 Hz establishes the presence of a P=C 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.