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The reaction of Cp(CO) 2 (NO)Cr with Me 3 P = CH 2  yields the tetramethylphosphonium -[(trimethylphosphoranyliden)acetyl-Chromate] Me 4 P[Cp(CO)(NO)Cr-C(O)-CH = PMe 3 ] (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-CH 2 PMe 3  (2) on photolysis. In the presence of Mel, 1 is degradated to [Me 4 P]I, [Me 3 PEt]I, [Me 2 PEt 2 ]I and Cp(CO) 2 (NO)Cr. Treatment of 1 with an equimolar amount of MeOSO 2 F leads to the formation of the "zwitterionic" phosphoniovinyl complexes Cp(CO)(NO)Cr-C(OMe) = CH-PMe 3  (3a) and Cp(CO)(NO)Cr-C(OMe) = C(Me)-PMe 3  (3b). With excess MeOSO 2 F the phosphoniocarbene complex [Cp(CO)(NO)Cr = C(OMe)-CH(Me)-PMe 3 ]SO 3 F (4a) is obtained. Me 3 P = CH 2  de-protonates 4a to 3b, which adds HCl to give [Cp(CO)(NO)Cr=C(OMe)-CH(Me)-PMe 3 ]Cl (4b). The phosphonium cobaltacylates Me 4 P[(CO)(NO)(L)CO-C(O)-CH = PMe 3 ] (5a, b), generated from the cobalt complex (CO) 2 (NO)(L)Co (L = CO, Me 3 P) and Me 3 P = CH 2 , readily transform to the ylide complexes (CO)(NO)(L)Co-CH 2 -PMe 3  (6a, b). MeX (X = I, SO 3 F) cleaves 6b to give (CO) 2 (NO)(Me-P)Co and [Me 3 PEt]X. The new complexes are characterized by elementary analysis and spectroscopy.

zeitschrift für naturforschung b

Zur Reaktion von Metall-koordiniertem Kohlenmonoxid mit Yliden, X [1] β-Phosphoniocarben-, β-Phosphonio vinyl-und Phosphor-Ylid-Komplexe des Chroms und Cobalts aus Tetramethylphosphonium- [(trimethylphosphoranyliden)acetyl-metallaten] / Reactions of Metal Coordinated Carbon Monoxide with Ylides, X [1] β-Phosphoniocarbene, β-Phosphoniovinyl and Phosphorus Ylide Complexes of Chromium and Cobalt Deriving from Tetramethylphosphonium [(trimethylphosphoranyliden)- acetyl-metallates]