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Several early-late heterodimetallaborane clusters have been isolated and structurally characterized through spectroscopic and crystallographic analysis. The thermolysis of [Cp2Zr(BH4)2] (Cp = η5-C5H5) with [Cp*IrB3H9] (Cp* = η5-C5Me5) and [(Cp*Rh)2B2H6] yielded arachno-[(Cp2Zr)(Cp*Ir)B3H9] ( 2) and arachno-[(Cp2Zr)(Cp*Rh)B4H10] ( 4), respectively. In a similar fashion, the reaction of [Cp2Hf(BH4)2] was performed with the same set of group 9 metallaboranes that led to the formation of arachno-[(Cp2Hf)(Cp*M′)B4H10] ( 5: M′ = Ir; 6: M′ = Rh). To the best of our knowledge, 2 is the first structurally characterized pentaborane(11) analogue containing zirconium, while the clusters 5 and 6 are the first examples with Hf in a hexaborane(12) core. The bonding between the Zr atoms and the boron ring was studied computationally by DFT methods, and 2 can be defined as a dimetallic analogue of arachno-B5H11 on the basis of the combined experimental and computational results. [ABSTRACT FROM AUTHOR]

Treatment of [Cp*IrCl2]2 (Cp* = pentamethylcyclopentadienyl) with Li[BH3(SePh)] at room temperature led to the isolation of a dimetala analogue of hexaborane(10), nido-[(Cp*Ir)(µ-SePh)2Ir{(Cp*Ir)SePh}B4H8] ( 1). Solid-state X-ray structure analysis of 1 showed an extended sandwich molecule with two iridium atoms between Cp* and a [B4Ir] ring. Further, in an effort to synthesize the Rh analogue of 1 under similar reaction conditions, we isolated arachno-[{(Cp*Rh)(µ-SePh)3}Rh(µ-SePh)B3H6] ( 2), a rhodium analogue of tetraboarane(10) in which the {RhB3} unit shows geometric equivalence with a metal π-allyl {MC3} species. Ir complex 1, having an Ir-Ir bond, can be considered similar to the dizinc sandwich complex [Cp*Zn-ZnCp*] in terms of the valence electron count at the metal centers. [ABSTRACT FROM AUTHOR]

A combined experimental and quantum-chemical study of a series of homometallic metallaheteroboranes [(Cp*M)2-E6B2H2] (M = Rh or RuH; E = S or Se; Cp* = η5-C5Me5), which are analogues of 1,3-bishomocubane, is reported. The thermolysis of nido-[(Cp*Rh)2B3H7] (1) in the presence of S or Se powder in toluene yielded bishomocubane clusters [(Cp*Rh)2-(μ-E)2(μ3-E)4B2H2], (3: E = S; 4: E = Se). In a similar fashion, the treatment of nido-[(Cp*RuH)2B3H7] (2) with S or Se powder in p-xylene yielded [(Cp*Ru)2(μ-E)2(μ3-E)4B2H2] (5: E = S; 6: E = Se) and [(Cp*Ru)2(μ3-Se)(μ4-Se)B3H5] (7). One of the noteworthy features of 3-6 is the presence of an electronprecise trichalcogenoborato ligand. All of the compounds have been characterized by mass spectrometry; IR spectroscopy; and 1H, 11B, and 13C NMR spectroscopy. The structures of 3, 4, 6, and 7 were established unequivocally by Xray crystallographic analysis. Quantum-chemical calculations by DFT methods for 3, 4, and 6 showed reasonable agreement with the experimentally observed structural parameters. The large HOMO-LUMO gaps are consistent with the high stabilities of these complexes. [ABSTRACT FROM AUTHOR]