Supraicosahedral polyhedra in metallaboranes: synthesis and structural characterization of 12-, 15-, and 16-vertex rhodaboranes

Roy, Dipak Kumar ; Mondal, Bijan ; Shankhari, Pritam ; Anju, R. S. ; Geetharani, K. ; Mobin, Shaikh M. ; Ghosh, Sundargopal (2013) Supraicosahedral polyhedra in metallaboranes: synthesis and structural characterization of 12-, 15-, and 16-vertex rhodaboranes Inorganic Chemistry, 52 (11). pp. 6705-6712. ISSN 0020-1669

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Official URL: http://pubs.acs.org/doi/abs/10.1021/ic400761z

Related URL: http://dx.doi.org/10.1021/ic400761z

Abstract

Syntheses and structural characterization of supraicosahedral rhodaborane clusters are reported. Reaction of [(Cp*RhCl2)2], (Cp* = η5-C5Me5) with [LiBH4·thf] followed by thermolysis with excess of [BH3·thf] afforded 16-vertex closo-[(Cp*Rh)3B12H12Rh{Cp*RhB4H9}], 1, 15-vertex [(Cp*Rh)2B13H13], 2, 12-vertex [(Cp*Rh)2B10Hn(OH)m], (3a: n = 12, m = 0; 3b: n = 9, m = 1; 3c: n = 8, m = 2) and 10-vertex [(Cp*Rh)3B7H7], 4, and [(Cp*Rh)4B6H6], 5. Cluster 1 is the unprecedented 16-vertex cluster, consists of a sixteen-vertex {Rh4B12} with an exo-polyhedral {RhB4} moiety. Cluster 2 is the first example of a carbon free 15-vertex supraicosahedral metallaborane, exhibits icosihexahedron geometry (26 triangular faces) with three degree-six vertices. Clusters 3a-c have 12-vertex isocloso geometry, different from that of icosahedral one. Clusters 4 and 5 are attributed to the 10-vertex isocloso geometry based on 10-vertex bicapped square antiprism structure. In addition, quantum-chemical calculations with DFT methods at the BP86 level of theory have been used to provide further insight into the electronic structure and stability of the optimized structures which are in satisfactory agreement with the structure determinations. All the compounds have been characterized by IR, 1H, 11B, 13C NMR spectroscopy in solution, and the solid state structures were established by crystallographic analysis of compounds 1–5.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:110756
Deposited On:31 Jan 2018 12:30
Last Modified:31 Jan 2018 12:30

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