87085-42-5Relevant articles and documents
Reactions of Metal Coordinated Carbon Monoxide with Ylides, X. β-Phosphoniocarbene, β-Phosphoniovinyl and Phosphorus Ylide Complexes of Chromium and Cobalt Deriving from Tetramethylphosphonium
Malisch, Wolfgang,Blau, Herbert,Weickert, Peter,Griessmann, Karl-Heinz
, p. 711 - 718 (2007/10/02)
The reaction of Cp(CO)2(NO)Cr with Me3P=CH2 yields tetramethylphosphonium- Me4P (1) via ylide addition at the carbonyl carbon and transylidation.A reversible equilibrium is established between 1 and the starting materials, which is responsible for the facile conversion of 1 into the ylide complex Cp(CO)(NO)Cr-CH2PMe3 (2) on photolysis.In the presence of MeI, 1 is degradated to I, I, I and Cp(CO)2(NO)Cr.Treatment of 1 with an equimolar amount of MeOSO2F leads to the formation of the zwitterionic phosphoniovinyl complexes Cp(CO)(NO)Cr-C(OMe)=CH-PMe3 (3a) and Cp(CO)(NO)Cr-C(OMe)=C(Me)-PMe3 (3b).With excess MeOSO2F the phosphoniocarbene complex SO3F (4a) is obtained.Me3P=CH2 deprotonates 4a to 3b, which adds HCl to give Cl (4b).The phosphonium cobaltacylates Me4P (5a, b), generated from the cobalt complex (CO)2(NO)(L)Co (L = CO, Me3P) and Me3P=CH2, readily transform to the ylide complexes (CO)(NO)(L)Co-CH2PMe3 (6a, b).MeX (X = I, SO3F) cleaves 6b to give (CO)2(NO)(Me3P)Co and X.The new complexes are characterized by elementary analysis and spectroscopy. - Keywords: Carbonmonoxide Conversion, Vinyl Complexes, Carbene Complexes, Ambidentate Nucleophilic Reactivity
