TY - JOUR
T1 - 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]–
AU - Wynd, Andrew J.
AU - Welch, Alan J.
AU - Parish, R. V.
PY - 1990
Y1 - 1990
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=51149206829&partnerID=8YFLogxK
U2 - 10.1039/DT9900002185
DO - 10.1039/DT9900002185
M3 - Article
AN - SCOPUS:51149206829
SN - 0300-9246
SP - 2185
EP - 2193
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 7
ER -