The cleavage of coordinated heterocumulenes. The reactions of [Fe(CO)(2)(PPh3)(2)(eta-SCY)] and their analogues with [Co(eta-C5H5)(PPh3)(2)] to give heteronuclear [{Co(eta-C5H5)}(2){Fe(CO)(2)(PPh3)}(mu(3)-S)(mu(3)-CY)] (Y = S or SR+) and related clus

摘要

The reaction of [Fe(CO)(2)(PPh3)(2)(eta(2)-CS2)] with two equivalents of [Co(eta-C5H5)(PPh3)(2)] gives [{Co(eta-C5H5)}(2)(Fe(CO)(2)(L)}(mu(3)-S)(mu(3)-CS)] (L=PPh3) as the sole product in good yield. Under the same conditions, [Fe(CO)(2)(L)(2)(eta(2)-CS2Me)][SO3CF3] gives [{Co(eta-C5H5)}(2){Fe(Co)(2)(L)}(mu(3)-S)(mu(3)-CSMe)][SO3CF3] The PPh3 ligand of [{Co(eta-C5H5)}(2)(Fe(CO)(2)(L)}(mu(3)-S)(mu(3)-CS)] (L = PPh3) may be replaced by P(OPh)(3) and P(OMe)(3) on UV photolysis to give the complexes where L = P(OPh)(3) and P(OMe)(3), but no isolable products were formed when L = CO, CNMe, PMe3 or PBu3". The three clusters react with RI and ROSO2CF3 (R = Me, Et or allyl) to give [{Co(eta-C5H5)}(2){Fe(CO)(2)(L)}(mu(3)-S)(mu-CSR)]+ salts, and there is spectroscopic evidence for the formation of the [{Co(eta-C5H5)}(2)(Fe(CO)(2)(PPh3)}(mu(3)-S)(mu(3)-CSMe2)](2+) cation. The molecular structures of [{Co(eta-C5H5)}(2)(Fe(CO)(2)(PPh3))(mu(3)-S)(mu(3)-CS)] and [{Co(eta-C5H5)}(2){Fe(CO)(2)(PPh3)}(mu(3)-S){mu(3)-CSMe}][I] have been determined by X-ray diffraction methods, and shown to be based on a Co2Fe triangle capped on one face by a mu(3)-S ligand and on the other face by a mu(3)-CS or mu(3)-CSMe+ ligand acting as a two-electron donor to the cluster. In the salt there are two cations whose structures differ slightly. In general, bond lengths are normal, but those to iron are always longer than those to cobalt. (C) 1998 Elsevier Science S.A. [References: 20]