화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.126, No.10, 3203-3217, 2004
Synthesis and characterization of hypoelectronic rhenaboranes. Analysis of the geometric and electronic structures of species following neither borane nor metal cluster electron-counting paradigms
The reaction of (Cp*ReH2)(2)B4H4 With monoborane leads to the sequential formation of (Cp*Re)(2)BnHn (n = 7-10, 1-4). 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)(2)B7H9 (5), is isolated that bears the same structural relationship to arachno-B9H15 as 1-4 bear to the closo-borane anions. Chloroborane permits the isolation of (Cp*ReH)(2)B5C15 (6), an isoelectronic chloroanalogue of known open (Cp*WH2)(2)B5H5 and (Cp*Re)(2)B6H4CI2 (7), a triple-decker complex containing a planar, six-membered 1,2-B6H4CI2 ring. Both are putative five- and six-boron intermediates in the formation of 1. Electronic structure calculations (extended Huckel and density functional theory) yield geometries in agreement with the structure determinations, large HOMO-LUMO gaps in accord with the high stabilities, and B-11 chemical shifts accurately reflecting the observed shifts. Analyses of the bonding in 1-4 reveal that the Cp*(ReCp)-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 (ReRe)-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 1-4 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.