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Chemistry and reactivity of dimolybdathiaborane, [(CpMo)BSH], 1, obtained from the reaction of 2-mercaptobenzothiazole, [CpMoCl] and [LiBH.thf], has been explored with dinuclear metal carbonyl [Fe(CO)]. As a result, reaction of 1 with [Fe(CO)] yielded heterometallathiaborane, [(CpMo)BHSFe(CO)], 2 in good yield. Both the new compounds have been characterized in solution by H, B and C NMR spectroscopy and the structural types were unequivocally established by X-ray crystallographic analysis of compound 2. Cluster 2 has a bicapped octahedral geometry with the {Fe(CO)} fragment occupying one of the high-connectivity cluster vertexes rather than a capping position. Interestingly, cluster 1 undergoes geometric changes (bicapped trigonal bipyramid → bicapped octahedron) on the addition of two-electron {Fe(CO)} fragment to 1. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Metal assisted borane condensationmethod has been employed forthe preparation of novel metallaborane cluster containing group 4metal. Pyrolysis of [Cp*IrB3H9], 1, with in situ generated zirconium bisborohydrate [Cp2Zr(BH4)2], produced from the fast metathesisreaction of [Cp2ZrCl2] and LiBH4,and excess of BH3·THF yielded arachno-[(Cp2Zr)(Cp*Ir)B4H10], 2, in 56% yield. Compound 2constitutes the first crystallographicstructure determination of hexaborane(12) metal analogue containingzirconium. The observed geometry of 2can be generatedfrom a dodecahedron by removing two vertices and an edge. Anticipatinga straight metal fragment substitution/addition reaction, mild thermolysisof 2with [Fe2(CO)9] was carriedout. However, the reaction led to the formation of known trimetallic[Cp*IrFe2(CO)9] cluster via cluster degradation.In addition, density functional theory (DFT) calculations have beencarried out for 2and other hypothetical early–latecombinations of hexaborane(12) metal analogues to reveal the electronicstructures. [ABSTRACT FROM AUTHOR]