Versatile N2S2 nickel-dithiolates as mono- and bridging bidentate, S-donor ligands to gold(I).

Development of square planar cis-dithiolate nickel complexes as metallo S-donor ligands focuses on the synthesis and structures of gold(I) heterometallic clusters derived from assemblage with three NiN2S2 complexes: Ni(bme-daco), Ni(bme-dach) and Ni(ema)(2-) (bme-daco = (bismercaptoethanediazacyclooctane); bme-dach = bismercaptoethanediazacycloheptane; and ema = N,N'-ethylenebis-2-mercaptoacetamide). With Ph3PAuCl as the gold source, examples of simple S-aurolation retaining the PPh3 on Au(+) were obtained for [{Ni(bme-daco)}AuPPh3](+)Cl(-) and [{Ni(ema)}2Au4(PPh3)4], where the latter complex demonstrated unsupported aurophilic interactions between [{Ni(ema)}Au2(PPh3)2] units in its X-ray crystal structure (Au-Au = 3.054 and 3.127 Å). Three compounds containing fully-supported digold units with Au-Au distances in the aurophilic range of 3.11 to 3.13 Å were found as stair-step structures in which planar NiN2S2 step treads are connected by planar S2Au2S2 risers at ca. 90°: [{Ni(bme-daco)}2Au2](2+)(Cl(-))2; [{Ni(bme-dach)}2Au2](2+)(Cl(-))2; and (Et4N(+))2[{Ni(ema)}2Au2](2-). Electrochemical data from cyclic voltammograms demonstrated a positive shift in Ni(II/I) couples for the [{NiN2S2}xAuy] complexes as compared to the NiN2S2 precursors and a ca. 700 mV decrease in communication between multiple NiN2S2 units as compared to [{NiN2S2}2Ni](2+) analogues in slant chair conformation. The analogy between NiN2S2 metallodithiolate ligands and diphosphine ligands holds here as in other examples of inorganic and organometallic complexes.