Issue 21, 2000

The solid state aggregation of two gold(I) nitrate complexes

Abstract

(Trimethylphosphine)gold(I) nitrate was prepared from the reaction of (Me3P)AuCl and AgNO3 in MeOH–CH2Cl2. Single crystals from CH2Cl2pentane contain trimers [(Me3P)Au(ONO2)]3 as sub-units of polymeric chains. The organization is based on short aurophilic Au–Au contacts. A discussion considering all other known (Me3P)AuX structures leads to the conclusion that small, electronegative anions X favour aurophilic multi-coordination with longer Au  Au contacts, while less electronegative, bulky groups X induce dimerization with short Au  Au contacts. In all cases neighbouring molecules are arranged with their principal axes roughly perpendicular (staggered). Crystals of (tBuNC)Au(ONO2) grown from CH2Cl2pentane at −25 °C were shown to be a 2∶1 dichloromethane solvate with a new meander-type structure, which is stable only at low temperature and under the standard pressure of a dichloromethane atmosphere. The structure is based on aurophilic interactions of a similar nature as in the solvent-free phase (obtained at 5 °C) as judged from the bond distance parameters, but the solvent molecules are accommodated in cavities formed through a different puckering of the chains. A comparison with other structures of (RNC)AuX molecules suggests that the parallel (eclipsed) head-to-tail alignment of the molecules is the preferred organization in the absence of other structure-determining effects.

Supplementary files

Article information

Article type
Paper
Submitted
03 May 2000
Accepted
12 Jun 2000
First published
20 Sep 2000

J. Chem. Soc., Dalton Trans., 2000, 3881-3884

The solid state aggregation of two gold(I) nitrate complexes

T. Mathieson, A. Schier and H. Schmidbaur, J. Chem. Soc., Dalton Trans., 2000, 3881 DOI: 10.1039/B003523H

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