Gold Clustering at Dimethylsulfoximine Me2S(0)NH

Polyaurated complexes of the dimethylsulfoximide anion [Me2S(0 )N]_ have been prepared by reacting N-trimethylsilyl-dimethylsulfoximide with [(Ph3P)Au]BF4 in various molar ratios. With one or two equivalents of the gold(I) reagent only the dinuclear complex is obtained in high yield: {[(Ph3P)Au]2NS(0 )Me2}+ BF4. With three or four equivalents only the trinuclear complex is produced: {[(Ph3P)Au]3NS(0 )Me2}2+ 2 BF4. No monoor tetra-auration was observed, respectively. The composition of the compounds has been confirmed by ana­ lytical and spectroscopic data, and the crystal structure of the dinuclear compound has been determined by single crystal X-ray diffraction of the dichloromethane solvate. The two gold atoms are found to be coordinated to the nitrogen atom with a small Au-N-Au angle of only 92.3(3)° and a short Au-Au distance of 2.9900(5) A. The nitrogen atom is in a distorted trigonal pyramidal configuration which allows an intramolecular SO-Au contact. For the trinuclear complex a structure with a tetracoordinate nitrogen atom [SNAU3] is proposed which is analogous to the corresponding complexes of phosphinimines R3P=NH. With the ditertiary phosphine Ph2PCH2Ch2PPh2 (dppe) a cyclic dinuclear complex (dppe)Au2[NS(0 )Me2]BF4 can be synthesized starting from (dppe)Au2Cl2. The reaction of the phosphine-rich precursor [(Ph3P)2Au]BF4 with Me3SiNS(0 )Me2 in the molar ratio 2:1 affords a binuclear complex {[(Ph3P)2Au]2NS(0 )Me2}BF4 of an as yet unknown structure.