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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]

In an attempt to synthesize expanded-cage metallaheteroboranes containing heavier chalcogen atoms, the reaction of diruthenaborane analogue of pentaborane(9), nido -[1,2-(Cp*RuH) 2 B 3 H 7 ] ( 1 ) with phenyl-chalcogenoborates Li[BH 3 (EPh)] (E = S, Se or Te) was carried out. Thermolysis of nido - 1 with Li[BH 3 (SPh)] led to the formation of the dimetalla-pentaborane(11) analogue arachno -[(Cp*Ru) 2 B 3 H 8 (SPh)] ( 2 ). In parallel to the formation of 2 , the reaction also yielded three B-H functionalized compounds, namely [(Cp*Ru) 2 B 4 H 7 (Ph)] ( 3 ), [(Cp*Ru) 2 B 4 H 7 (Cl)] ( 4 ) and [(Cp*Ru) 2 B 4 H 6 (SPh)(Cl)] ( 5 ). On the other hand, reaction of 1 with Li[BH 3 (SePh)] led to the formation of the diruthenium analogue of hexaborane(10) nido -[(Cp*Ru) 2 B 4 H 9 (SePh)] ( 6 ), whereas Li[BH 3 (TePh)] yielded the capped nido -pentagonal-pyramidal [(Cp*Ru) 2 B 4 H 6 Te] ( 7 ). Compound 7 is a rare ruthenaborane cluster containing a heavier chalcogen element (Te). All the compounds were characterized by mass spectrometry and 1 H, 1 H{ 11 B}, 11 B{ 1 H} and 13 C{ 1 H}NMR spectroscopy. The solid state X-ray structures of all the compounds were unequivocally established by crystallographic analysis. Additionally, the electronic properties of compound 2 were analyzed. [ABSTRACT FROM AUTHOR]