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

Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, TN, India
Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes)-UMR 6226, F-35000 Rennes, France
Author to whom correspondence should be addressed.
Inorganics 2019, 7(3), 27;
Received: 29 January 2019 / Revised: 13 February 2019 / Accepted: 14 February 2019 / Published: 26 February 2019
(This article belongs to the Special Issue Binuclear Complexes)
PDF [4078 KB, uploaded 26 February 2019]


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], 13 (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 15 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. View Full-Text
Keywords: chromaborane; metallaborane; mixed-metal cluster; molybdaborane; tungstaborane chromaborane; metallaborane; mixed-metal cluster; molybdaborane; tungstaborane

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Bag, R.; Saha, S.; Borthakur, R.; Mondal, B.; Roisnel, T.; Dorcet, V.; Halet, J.-F.; Ghosh, S. Synthesis, Structures and Chemistry of the Metallaboranes of Group 4–9 with M2B5 Core Having a Cross Cluster M–M Bond. Inorganics 2019, 7, 27.

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