Collect. Czech. Chem. Commun. 2005, 70, 430-440

Macropolyhedral Boron-Containing Cluster Chemistry. A Metallathiaborane from S2B17H17: Isolation and Characterisation of [(PMe2Ph)2PtS2B16H16]; A neo-arachno Ten-Vertex Cluster Shape, and the Constitution of the [arachno-B10H15]- Anion

Michael J. Carra,b, Michael G. S. Londesborougha, Jonathan Bouldb, Ivana Císařovác, Bohumil Štíbra and John D. Kennedyb,*

a Institute of Inorganic Chemistry, Academy of Sciences of the Czech Republic, 250 68 Řež near Prague, Czech Republic
b The School of Chemistry of the University of Leeds, Leeds, UK LS2 9JT, England
c Faculty of Science, Charles University, Hlavova 2030, 128 42 Prague 2, Czech Republic


The deprotonation of S2B17H17 with sodium hydride and subsequent reaction with [PtCl2(PMe2Ph)2] gives the new macropolyhedral metallathiaborane [(PMe2Ph)2PtS2B16H16], of which the cluster consists of a conventional eleven-vertex nido {SB10} unit, fused, with two boron atoms in common, with a {PtSB8} unit of unique ten-vertex neo-arachno constitution and geometry. The latter geometry suggests a configuration for the previously structurally uncharacterised [B10H15]- anion; starting from this configuration, DFT calculations of structure and thence of boron nuclear shieldings, which are found very closely to mimic those found experimentally, thence support a fluxional structure for [B10H15]- with three {BHB(bridging)} and two {BH(endo)} hydrogen atoms around a six-membered open face.

Keywords: Macropolyhedral; neo-arachno ten-vertex cluster; X-Ray diffraction; Crystal structure; Platinum-sulfur-polyboron cluster; Sulfur-platinum-polyboron cluster; Metallaboranes; Boranes; Metallathiaborane; Thiametallaboranes; Borane anions; DFT calculations.

References: 40 live references.