26720-22-9Relevant articles and documents
Dinuclear μ-alkylidene complexes of transition metals as models for the transformation of CH2X2 (X=Cl, Br, I) into malonic acid derivatives by double carbonylation reactions
Denise, B.,Navarre, D.,Rudler, H.,Daran, J. C.
, p. 273 - 289 (2007/10/02)
The carbonylation of the μ-alkylidene complexes Fe2(CO)8CH2 (1) and Pd2I2(PPh2CH2PPh2)2CH2 (2) has been studied under a variety of conditions.In the presence of an alcohol ROH, complex 1 gives mainly the acetate CH3CO2R, the product of monocarbonylation, whereas under the same conditions complex 2 gives the malonate CH2(CO2R)2, the product of dicarbonylation.The mechanisms of both reactions are discussed.From the fraction involving 1 a mononuclear complex resulting from the dimerization of ketene has been isolated, and its structure established by an X-ray diffraction study.Olefins such as ethene and norbornene are able to trap the ketene intermediate.The possible participation of such μ-alkylidene complexes in the direct transformation of CH2X2 (X=Cl, Br, I) into malonic acid derivatives is discussed.
CARBONYLATION DES COMPLEXES μ-ALKYLIDENIQUES: MISE EN EVIDENCE D'UN COMPOSE MINEUR PROVENANT D'UNE DOUBLE INSERTION DE CO
Navarre, D.,Rose-Munch, F.,Rudler, H.
, p. C15 - C18 (2007/10/02)
While the μ-alkylidenetungsten complex, (CO)9W2CHCH=C(CH3)2 gives the expected ester resulting from CO insertion-solvolysis reactions, the μ-alkylideneiron complex (CO)8Fe2CH2 gives, as well as the expected ester, a malonate formed by double carbonylation of the bridging carbon atom.
