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Synthesis and Characterization of Hypoelectronic Rhenaboranes. Analysis of the Geometric and Electronic Structures of Species Following Neither Borane nor Metal Cluster Electron-Counting Paradigms
, Le Guennic Boris, Jiao Haijun, Kahlal Samia, Saillard Jean-Yves, Halet Jean-François, Shang Maoyu, M. Beatty Alicia, L. Rheingold Arnold, P. Fehlner Thomas
Published in American Chemical Society (ACS)
2004
Volume: 126
   
Issue: 10
Pages: 3203 - 3217
Abstract

The reaction of (Cp*ReH2)2B4H4 with monoborane leads to the sequential formation of (Cp*Re)2BnHn (n = 7−10, 14). These species adopt closed deltahedra with the same total connectivities as the closo-borane anions [BnHn]2-, n = 9−12, but with flattened geometries rather than spherical shapes. These rhenaborane clusters are characterized by high metal coordination numbers, Re−Re cross-cluster distances within the Re−Re single bond range, and formal cluster electron counts three skeletal electron pairs short of that required for a canonical closo-structure of the same nuclearity. An open cluster, (Cp*ReH)2B7H9 (5), is isolated that bears the same structural relationship to arachno-B9H15 as 14 bear to the closo-borane anions. Chloroborane permits the isolation of (Cp*ReH)2B5Cl5 (6), an isoelectronic chloro-analogue of known open (Cp*WH2)2B5H5 and (Cp*Re)2B6H4Cl2 (7), a triple-decker complex containing a planar, six-membered 1,2-B6H4Cl2 ring. Both are putative five- and six-boron intermediates in the formation of 1. Electronic structure calculations (extended Hückel and density functional theory) yield geometries in agreement with the structure determinations, large HOMO−LUMO gaps in accord with the high stabilities, and 11B chemical shifts accurately reflecting the observed shifts. Analyses of the bonding in 14 reveal that the Cp*Re···Cp*Re interaction generates fragment orbitals that are able to contribute the “missing” three skeletal electron pairs required for skeletal bonding. The necessity of a Re···Re interaction for strong cluster bonding requires a borane fragment shape change to accommodate it, thereby explaining the noncanonical geometries. Application of the debor principle of borane chemistry to the shapes of 14 readily rationalizes the observed geometries of 5 and 6. This evidence of the scope of transition metal fragment control of borane geometry suggests the existence of a large class of metallaboranes with structures not found in known borane or metal clusters.

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PublisherData powered by TypesetAmerican Chemical Society (ACS)
Open AccessNo