In:
European Journal of Inorganic Chemistry, Wiley, Vol. 2010, No. 13 ( 2010-05), p. 2044-2053
Abstract:
The 1:1 tribenzylphosphane (PBn 3 ) complexes of gold(I)[(Bn 3 P)AuX] (X = Cl and Br) have been synthesised, and their structures were determined by single‐crystal X‐ray crystallography. The compounds are isomorphous, neutral molecules with linearly coordinated P–Au–X arrays. Each structure contains three independent [(Bn 3 P)AuX] entities lying on the three threefold axes of space group P 3 c 1. The mean bond lengths are Au–Cl 2.302(8), Au–P 2.227(11) Å for the chloride and Au–Br 2.404(10), Au–P 2.229(4) Å for the bromide. These contrast with the 1:1 adducts previously reported for copper(I), which take the form [Cu(PBn 3 ) 2 ][CuX 2 ]. The 1:2 AuX:PBn 3 compounds that have been synthesised are formulated as [Au(PBn 3 ) 2 ]X · n H 2 O (X = Cl, n = 1 or 2; X = I and BF 4 , n = 0). Single‐crystal X‐ray structures show that linearly two‐coordinate centrosymmetric [Au(PBn 3 ) 2 ] + arrays are found in [Au(PBn 3 ) 2 ]Cl · H 2 O and [Au(PBn 3 ) 2 ]BF 4 with Au–P bond lengths of 2.2988(7) and 2.3016(7) Å for the chloride and 2.2975(7) Å for the tetrafluoroborate. ν(AuX) bands in the far‐IR spectra of [(Bn 3 P)AuX] are assigned at 320 and 227 cm –1 for X = Cl and X = Br, respectively. The 31 P CP MAS NMR spectra of [(Bn 3 P)AuX] (X = Cl, Br) and [Au(PBn 3 ) 2 ]X (X = Cl · H 2 O, Cl · 2H 2 O, I, BF 4 ) are reported, and the observation of 2 J (PP) coupling in the spectrum of [Au(PBn 3 ) 2 ]Cl · 2H 2 O is consistent with the presence in this complex of noncentrosymmetric cations in which the two phosphorus atoms are inequivalent.
Type of Medium:
Online Resource
ISSN:
1434-1948
,
1099-0682
DOI:
10.1002/ejic.v2010:13
DOI:
10.1002/ejic.200901209
Language:
English
Publisher:
Wiley
Publication Date:
2010
detail.hit.zdb_id:
1475009-0
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