title: Monohaloboryls (BHX-) as bridging ligands: observable dinuclear σ-(halo)boranyl intermediates in the synthesis of metalloborylenes.
abstract: Upon treating transition-metal-dihaloboryl complexes of the form [L(n)MBX(2)] with K[(η(5)-C(5)H(5))MnH(CO)(2)], salt elimination occurs along with a migration of the Mn-bound hydride ligand onto the boron atom, thereby forming dinuclear σ-(halo)boranyl complexes of the form [L(n)M(μ-BHX)Mn(CO)(2)(η(5)-C(5)H(5))]. Most of these complexes react further at room temperature to lose HX and provide metalloborylene complexes [L(n)M-B = Mn(CO)(2)(η(5)-C(5)H(5))]; however, when ML(n) = Re(CO)(5) the σ-(halo)boranyl complex decomposes into unidentifiable products. We found through DFT calculations that two electronically and structurally distinct forms of the intermediate σ-(halo)boranyl complexes exist, one of which easily loses HX and one that does not.
authors.affiliation: Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
authors.forename: Jürgen
authors.initials: J
authors.lastname: Bauer
authors.forename: Holger
authors.initials: H
authors.lastname: Braunschweig
authors.forename: Rian D
authors.initials: RD
authors.lastname: Dewhurst
authors.forename: Katharina
authors.initials: K
authors.lastname: Kraft
authors.forename: Krzysztof
authors.initials: K
authors.lastname: Radacki