title: Aminoborylene complexes of group 6 elements and iron: a synthetic, structural, and quantum chemical study.
abstract: 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). Structural and spectroscopic parameters were discussed with respect to the trans-effect of the borylene ligand and the degree of M-B d(pi)-p(pi)-backbonding. Computational studies were performed on Group 6-borylene complexes. The population and topological analyses as well as the molecular orbital composition are consistent with the presence of both sigma-and pi-type interactions. There are, however, indications that the d(pi)-p(pi)-backbonding in the silylborylene complex is significantly more pronounced than in the aminoborylene complexes.
authors: Institut für Anorganische Chemie, Bayerische Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
authors: Benoît
authors: B
authors: Blank
authors: Miriam
authors: M
authors: Colling-Hendelkens
authors: Carsten
authors: C
authors: Kollann
authors: Krzysztof
authors: K
authors: Radacki
authors: Daniela
authors: D
authors: Rais
authors: Katharina
authors: K
authors: Uttinger
authors: George R
authors: GR
authors: Whittell
authors: Holger
authors: H
authors: Braunschweig