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DOI: 10.1039/A702582C (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 2865-2868

Covalent radii of four-co-ordinate copper(I), silver(I) and gold(I): crystal structures of [Ag(AsPh3)4]BF4 and [Au(AsPh3)4]BF4

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Upendra M. Tripathi, Andreas Bauer and Hubert Schmidbaur

Abstract

The complexes [Ag(AsPh3)4]BF4 and [Au(AsPh3)4]BF4 were prepared from AgBF4 and 4 equivalents of AsPh3, and from equimolar quantities of [Au(AsPh3)Cl] and AgBF4 and 3 equivalents of AsPh3, respectively, in dichloromethane solution. Single crystals of the two compounds are isomorphous (trigonal, space group R[3 with combining macron], Z = 6) and contain cations with a tetrahedral Ag/Au–As4 core. From the Ag/Au–As distances measured at 199 K the covalent radii of four-co-ordinate silver(I) and gold(I) have been calculated using an accepted standard covalent radius for four-co-ordinate arsenic(III), r(AsIII) = 1.20 Å; r(AuI) = 1.37 Å is found to be 6% smaller than r(AgI) = 1.46 Å. This contraction reflects the strong influence of relativistic effects on atomic radii. From other data, r(CuI) for four-co-ordinate copper is estimated to be 1.29 Å.

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