Synthesis, structure, and bonding of novel homodinuclear cobalt and nickel borylene complexes.

Herein we report for the first time full details on the synthesis and structural characterization of novel homodinuclear bridging cobalt and nickel borylene complexes containing bridging carbonyl ligands, an unusual coordination motif rarely before observed for homodinuclear borylene complexes. Furthermore, the homodinuclear nickel complex represents the first instance of a nickel borylene complex. Quantum chemical analyses of charge-density topology, electron localization function (ELF) and natural charges indicate the absence of direct metal-metal bonds in both the cobalt and nickel systems, in contradiction with electron counting.

Aminoborylene complexes of group 6 elements and iron: a synthetic, structural, and quantum chemical study.

Transition-metal-borylene complexes of the type [(OC)(5)M=BR] {M=Cr, Mo, W; R=N(SiMe(3))(2), 1a-3a, Si(SiMe(3))(3), 4a} and [(OC)(4)Fe=B=N(SiMe(3))(2)] (8) were prepared by salt elimination reactions. Synthesis of the latter complex was accompanied by the formation of substantial amounts of an unusual dinuclear iron complex [Fe(2){mu-C(2)O(2)(BN(SiMe(3))(2))}(2)(CO)(6)] (9). The aminoborylene complexes of Group 6 metals were converted to trans-[(Cy(3)P)(CO)(4)M=B=N(SiMe(3))(2)] (5a-7a) by irradiation in the presence of PCy(3).