Mono- and dimetallic cyano complexes with {Mo(eta(3)-allyl)(CO)(2)(N-N)} fragments

Treatment of [MoCl(eta(3)-allyl)(CO)(2)(phen)] with NaCN in CH2Cl2/MeOH afforded [Mo(CN)(eta(3)-allyl)(CO)(2)(phen)] [allyl = C3H5 (1a); 2-MeC3H4 (1b)] as the sole products (no products of cyanide attack on the allyl group were detected). Treatment of 1a,b with [Mo(OTf)(eta(3)-C3H5)(CO)(2)(phen)] and NaBAr'(4) in CH2Cl2 yielded the compounds [{Mo(eta(3)- allyl)(CO)(2)(phen)}(mu-CN){Mo(eta(3)-C3H5)(CO)(2)(phen)}]BAr'(4) (2a,b). Analogous treatment of 1a with fac-[M(OTf)(CO)(3)(bipy)] (M = Mn, Re) and NaBAr'(4) resulted in the synthesis of [{Mo(eta(3)-C3H5)(CO)(2)(phen)}(mu-CN){M(CO)(3)(bipy)}]BAr'(4) (3, 4), in which the C and N atoms of the cyano bridge are bonded to Mo and M (M = Mn, Re), respectively. The linkage isomer of 4 (C and N atoms of the cyano group bonded to Re and Me, respectively) (6) was prepared by treatment of [Re(CN)(CO)(3)(bipy)] (5) with [Mo(OTf)(eta(3)-C3H5)(CO)(2)(phen)] and NaBAr'(4). Compounds 1a, 2b, 3, and 6 were characterized by X-ray diffraction. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).