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Synthesis and structure of dirhodium analogue of octaborane-12 and decaborane-14
Venkatachalam Ramkumar,
Published in
Volume: 51
Issue: 20
Pages: 10715 - 10722
We present the results of our investigation of a thermally driven cluster expansion of rhodaborane systems with BH 3·THF. Four novel rhodaborane clusters, for example, nido-[(CpRh) 2B 6H 10], 1; nido-[(CpRh)B 9H 13], 2; nido-[(CpRh) 2B 8H 12], 3; and nido-[(CpRh) 3B 8H 9(OH) 3], 4 (Cp* = η 5-C 5Me 5), have been isolated from the thermolysis of [CpRhCl 2] 2 and borane reagents in modest yields. Rhodaborane 1 has a nido geometry and is isostructural with [B 8H 12]. The low temperature 11B and 1H NMR data demonstrate that compound 1 exists in two isomeric forms. The framework geometry of 2 and 3 is similar to that of [B 10H 14] with one BH group in 2 (3-position), and two BH groups in 3 (3, 4-positions) are replaced by an isolobal {CpRh} fragment. The 11 vertex cluster 4 has a nido structure based on the 12 vertex icosahedron, having three rhodium and eight boron atoms. In addition, the reaction of rhodaborane 1 with [Fe 2(CO) 9] yielded a condensed cluster [(CpRh) 2{Fe(CO) 3} 2B 6H 10], 5. The geometry of 5 consists of [Fe 2B 2] tetrahedron and an open structure of [(CpRh) 2B 6], fused through two boron atoms. The accuracy of these results in each case is established experimentally by spectroscopic characterization in solution and structure determinations in the solid state. © 2012 American Chemical Society.
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JournalInorganic Chemistry
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