Some attempts to prepare five-co-ordinated gold(III) complexes. Crystal and molecular structures of [Au(C6H4CH2NMe2-2)(phen)(PPh3)][BF4]2·CH2Cl2, [Au(C6H4CH2NMe2-2)(NC9H6O)]BF4, and [Au(C6H4CH2NMe2-2)(H2NC6H4S)]ClO4

Abstract

Complexes [Au(dmp)(phen)]X₂[dmp = 2-(dimethylaminomethyl)phenyl, phen = 1,10-phenanthroline, X = BF₄ or ClO₄] react (i) with PR₃(R = Ph or C₆H₄OMe-p)(1:1) to give the five-co-ordinated complexes [Au(dmp)(phen)(PR₃)][BF₄]₂, (ii) with KCN (1:1) to give [Au(dmp)(CN)(phen)]BF₄, and (iii) with KCN and 1,2-bis(diphenylphosphino)ethane (dppe) to give [Au(dmp)(CN)(dppe)]ClO₄, which in turn reacts with [AuCl(tht)](tht = tetrahydrothiophene) to form the gold(I)–gold(III) complex [Au(dmp)(CN)(dppe)AuCl]ClO₄. Complexes [Au(dmp)(py)₂]X₂(py = pyridine) react with 8-hydroxyquinoline (NC₉H₆OH) or 2-aminothiophenol (H₂NC₆H₄SH) to form [A[graphic omitted])]BF₄ or [A[graphic omitted])]ClO₄ respectively; the crystal structures of these latter complexes show square-planar co-ordination of the gold atom with the phenyl group of dmp trans to oxygen or nitrogen respectively. The crystal structure of [Au(dmp)(phen)(PPh₃)][BF₄]₂·CH₂Cl₂ shows a distorted square-pyramidal co-ordination, with the basal plane containing Au and the donor atoms of dmp, PPh₃, and one phen N atom; the other N atom occupies a more distant axial position [Au–N 2.151(12), 2.154(8), and 2.627(10)Å].