Synthesis, Structures and Chemistry of the Metallaboranes of Group 4–9 with M₂B₅ Core Having a Cross Cluster M–M Bond

Abstract

In an attempt to expand the library of M2B5 bicapped trigonal-bipyramidal clusters with different transition metals, we explored the chemistry of [Cp*WCl4] with metal carbonyls that enabled us to isolate a series of mixed-metal tungstaboranes with an M2{B4M’} {M = W; M’ = Cr(CO)4, Mo(CO)4, W(CO)4} core. The reaction of in situ generated intermediate, obtained from the low temperature reaction of [Cp*WCl4] with an excess of [LiBH4·thf], followed by thermolysis with [M(CO)5·thf] (M = Cr, Mo and W) led to the isolation of the tungstaboranes [(Cp*W)2B4H8M(CO)4], 1⁻3 (1: M = Cr; 2: M = Mo; 3: M = W). In an attempt to replace one of the BH—vertices in M2B5 with other group metal carbonyls, we performed the reaction with [Fe2(CO)9] that led to the isolation of [(Cp*W)2B4H8Fe(CO)3], 4, where Fe(CO)3 replaces a {BH} core unit instead of the {BH} capped vertex. Further, the reaction of [Cp*MoCl4] and [Cr(CO)5·thf] yielded the mixed-metal molybdaborane cluster [(Cp*Mo)2B4H8Cr(CO)4], 5, thereby completing the series with the missing chromium analogue. With 56 cluster valence electrons (cve), all the compounds obey the cluster electron counting rules. Compounds 1⁻5 are analogues to the parent [(Cp*M)2B5H9] (M= Mo and W) that seem to have generated by the replacement of one {BH} vertex from [(Cp*W)2B5H9] or [(Cp*Mo)2B5H9] (in case of 5). All of the compounds have been characterized by various spectroscopic analyses and single crystal X-ray diffraction studies.

Keywords

• chromaborane
• metallaborane
• mixed-metal cluster
• molybdaborane
• tungstaborane