Gold Clustering at Dimethylsulfoximine Me2S(O)NH

Abstract

Abstract Gold Clustering, Dimethylsulfoximine Polyaurated complexes of the dimethylsulfoximide anion [Me2S(O)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(O)Me2}+ BF4 - . With three or four equivalents only the trinuclear complex is produced: {[(Ph3P)Au]3NS(O)Me2}2+ 2 BF4 - . No mono- or tetra-auration was observed, respectively. The composition of the compounds has been confirmed by analytical 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) Å. 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