Gold Coordination by 2‐(Diphenylphosphanyl)aniline

The reaction of 2‐(diphenylphosphanyl)aniline ( 1 ) with (tetrahydrothiophene)gold(I) chloride in the molar ratio 1:1 gives a stable molecular complex 2 , in which the gold atom is bonded to the phosphorus atom. Reaction of two equivalents of ligand 1 with one equivalent of the salt [(tht) 2 Au]ClO 4 results in the displacement of both thioether ligands, affording the ionic complex {[(2‐NH 2 C 6 H 4 )PPh 2 ] 2 Au} + ClO − 4 ( 3a ), in which the metal center is exclusively P‐coordinated. Treatment of [(tht) 2 Au]ClO 4 with ligand 1 (1:1) affords the mixed P/S‐coordinated complex 4 , the structure of which has been confirmed by single‐crystal X‐ray diffraction. The reaction of ligand 1 with [(Ph 3 P)Au] + BF − 4 leads to a mixture of products which are components of an equilibrium between the unsymmetrical salt {[(2‐NH 2 C 6 H 4 )PPh 2 ]Au(PPh 3 )} BF − 4 with the two symmetrical species 3b (the BF − 4 analogue of 3a ) and [(Ph 3 P) 2 Au] + BF − 4 , With {[(Ph 3 P)Au] 3 O} + BF − 4 as the aurating agent, the ligand 1 (molar ratio 1:1) is converted into a polynuclear complex 7 , which is tentatively assigned a structure with intimate aggregation of six gold atoms.