1. Chemistry of early and late transition metallaboranes: synthesis and structural characterization of periodinated dimolybdaborane [(Cp*Mo)2B4H3I5].
- Author
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Yuvaraj, K., Roy, Dipak Kumar, Arivazhagan, C., Mondal, Bijnaneswar, and Ghosh, Sundargopal
- Subjects
THERMOLYSIS ,CHEMICAL reactions ,ELECTRONS ,TRANSITION metals ,NUCLEAR magnetic resonance spectroscopy - Abstract
Thermolysis of an in situ generated intermediate [(Cp*Ta)
2 (BH3 )2 Cl2 ], 1 generated from the reaction of [Cp*TaCl4 ], (Cp* = η5 -C5 Me5 ) and [LiBH4 ·thf], in presence of [Ru3 (CO)12 ] yielded pileo-[Cp*TaCl(μ-Cl)-B2 H4 Ru3 (CO)8 ], 2 having two electrons fewer than seven pairs required for the observed square pyramidal geometry. Cluster 2 is the first example of an unsaturated cluster comprising early and late transition metals in a square pyramid core. This reaction also yielded [(Cp*Ta)2 (B2 H6 )(B2 H4 Cl2 )], 3 as a by-product. In addition, the reaction of [Cp*MoCl4 ] (Cp* = η5 -C5 Me5 ) with [LiBH4 .thf] in presence of excess [MeI] at mild condition led to the isolation of periodinated dimolybdatetraborane [(Cp*Mo)2 B4 H3 I5 ], 4 that hints a possible existence of [(Cp*Mo)2 B4 H8 ]. After the isolation of periodinated 4, we extended this chemistry towards the late transition metallaborane [(Cp*Rh)3 B4 H4 ], 5 using [PtBr2 ] as brominating source. Although all the attempts to isolate perbrominated rhodaborane failed, we have isolated partially brominated rhodaborane clusters [(Cp*Rh)3 (BH)-(BBr)3 ], 6 and [(Cp*Rh)3 (BH)3 (BBr)], 7. All the compounds were characterized by IR and1 H,11 B and13 C NMR spectroscopy in solution, and the solid-state structures of 2, 4 and 6 were established by crystallographic analysis. [ABSTRACT FROM AUTHOR]- Published
- 2015
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