Metal-bound thiolates show S-based reactivity including alkylation, oxygenation, and metallation.  We have studied the donating ability of a series of square planar,NiN2S2 complexes by reporter units such as tungsten carbonyls and dinitrosyl iron complexes.  In this way nickel cis-dithiolates may be described as metallo ligands, comparable to diphenylphosphinoethane or bipyridine.  Herein we describe the products of reaction of [NiN2S2 ]n (n = 0 or 2-) complexes with Ph3PAuCl, with expectation of a thiolate S-donor to the proton analogue Ph3PAu+. The N2S2Ni complex based on bismercaptoethanediazacyclooctane, yielded the expected 1:1 adduct, [Ni(bme-daco)AuPPh3]+Cl-.  However with the less sterically encumbered bismercaptoethane-diazacycloheptane ligand, as well as the tetraanionic N,N'-ethylenebis-2-mercaptoacetamide ligand, both the chloride and PPh3 were displaced by the metallodithiolates, with formation of tetrametallic [Au2{Ni(bme-dach)2}]2+(2Cl-) and (NEt4+)2[Au2{Ni(ema)2}]2-, in which aurophilic interactions are displayed within the S-bridging Au�Au units.  The oxidative addition reactions of RX and X2 will be compared to those of analogous di-gold(I) complexes.

?Cis-NiN<sub>2</sub>S<sub>2 </sub>?metallodithiolates as mono- and bidentate S-donors to gold (I)

245th National Meeting (2013)

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?Cis-NiN2S2 ?metallodithiolates as mono- and bidentate S-donors to gold (I)

?Cis-NiN₂S₂?metallodithiolates as mono- and bidentate S-donors to gold (I)