Journal of Organometallic Chemistry p. 17 - 26 (1985)
Update date:2022-08-03
Topics:
Fischer, Helmut
Maerkl, Robert
Zeuner, Siegfried
The pentacarbonyl[methoxy(phenyl)carbene]complexes (CO)5M[C(OMe)Ph][M = Cr (Ia), Mo (Ib), W (Ic) react with [(Ph3P)2N][NCBH3] to give the new nitrile complexes [(Ph3P)2N]+ {(CO)5M[NCC(OMe)(Ph)BH)3]}-. The reaction of Ic with NCSiMe3 yields (CO)5W[NCC(OMe)(Ph)SiMe3]; however, in the presence of silica gel (CO)5W[NCC(OMe)(Ph)H] is obtained. From the reaction of pentacarbonyl(diphenylcarbene)tungsten, (CO)5W[CPh2], with NCSnBun3 in diethyl ether, (CO)5W[NCCHPh2] was isolated. Formally, the new nitrile complexes correspond to the products of a coupled insertion: (a) of NC from RCN into the MC(R′)Ph bond of (CO)5M[C(R′)Ph] and (b) of C(R′)Ph into the CR bond of RCN. For RSiMe3 and SnBun3, subsequent hydrolysis of the initially formed complexes affords the R/H substitution products.
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