Synthesis and characterisation of second-generation metallodithiolene complexes of the type [Tp*ME(dithiolene)] (M = Mo, W; e = O, S) and a novel 'organoscorpionate' complex of tungsten

Abstract

Paramagnetic, chalcogenido-M(v) dithiolene complexes, [Tp*ME{S 2C2(CO2Me)2}] [M = Mo, E = O (1), S (2); M = W, E = O (3), S (4); Tp* = hydrotris(3,5-dimethylpyrazol-1-yl) borate] are generated in the reactions of dimethyl acetylenedicarboxylate (DMAC) and the sulfur-rich complexes NEt4[Tp*MoS(S4)] and NEt4[Tp*WS3]; the oxo complexes result from hydrolysis of the initial sulfido products. As well, a novel 'organoscorpionate' complex, [W{S2C2(CO2Me)2}{SC 2(CO2Me)2-Tp*}] (5), has been isolated from the reactions of NEt4[Tp*WS3] with excess DMAC. Complexes 1, 4 and 5 have been isolated and characterised by microanalytical, mass spectrometric, spectroscopic and (for 4 and 5) X-ray crystallographi..