Gold–boron chemistry. Part 2. The interaction of {AuP(C6H11)3} bridges with decaboranyl cages: the accurate structure of [5,6-µ-{AuP(C6H11)3}-nido-B10H13], and the synthesis and molecular and electronic structures of its conjugate base [5,6,9,10-µ4-{AuP(C6H11)3}-nido-B10H12]

Andrew J. Wynd, Alan J. Welch, R. V. Parish

Research output: Contribution to journalArticle

Abstract

Analysis of the results of an accurate, low-temperature redetermination of the molecular structure of [5,6-µ-{AuP(C6H11)3}-nido-B10H13](1a) implies an interaction, albeit weak, between the bridging gold atom and the B(9)H(9,10)B(10) moiety, and extended Hückel molecular orbital (EHMO) calculations reveal that the nature of this bonding is interaction of the three-centre two-electron–B(9)HB(10) unit with a previously vacant 6sp-hybrid orbital on gold. Mössbauer parameters obtained for (1a) are consistent with an sp-hybridised gold (I) atom which makes a supplementary weak interaction. Deprotonation of (1a) or of its P(C6H4Me-2)3 analogue removes the H(9,10) atom, and affords species (2) in which the gold–phosphine unit has slipped from µ to µ4 on a decaboranyl framework, the molecular structure of [NHEt3][nido-{AuP(C6H11)3}B10H12], (2a), having been established by a crystallographic stydy. For (2), a combination of Mössbauer spectroscopic studies and EHMO calculations indicates that the orbital number of the metal atom is again somewhat greater than 2, i.e. that the formal co-ordination geometry of the gold (I) bridge is intermediate bewteen linear and trigonal, but more so than in (1). The deprotonation of (1) is fully reversible, and its reaction with HCl results in cleavage of the remaining gold–boron connectivities to afford B10H14.
Original languageEnglish
Pages (from-to)2185-2193
Number of pages9
JournalJournal of the Chemical Society, Dalton Transactions
Issue number7
DOIs
Publication statusPublished - 1990

ASJC Scopus subject areas

  • Chemistry(all)

Fingerprint Dive into the research topics of 'Gold–boron chemistry. Part 2. The interaction of {AuP(C<sub>6</sub>H<sub>11</sub>)<sub>3</sub>} bridges with decaboranyl cages: the accurate structure of [5,6-µ-{AuP(C<sub>6</sub>H<sub>11</sub>)<sub>3</sub>}-<i>nido</i>-B<sub>10</sub>H<sub>13</sub>], and the synthesis and molecular and electronic structures of its conjugate base [5,6,9,10-µ<sub>4</sub>-{AuP(C<sub>6</sub>H<sub>11</sub>)<sub>3</sub>}-<i>nido</i>-B<sub>10</sub>H<sub>12</sub>]<sup>–</sup>'. Together they form a unique fingerprint.

Cite this