Four homoleptic insulating salts were crystallized using static galvanostatic oxidation of the organometallic donor (Cp)2W(dmit) (dmit2- = 1,3-dithiole-thione-4,5-dithiolate) in the presence of the anions BF4-, Br-, PF6- and Au(CN)2-.  Within these salts, containing a formally d1 cation, the W2S2C2 metallacycle at the S���S hinge is folded to varying extents, illustrating the non-innocent character of the dithiolate ligand.  Using Raman spectroscopy, spectra were measured for each of the four salts as well as the neutral donor to search for a correlation between the angle of the fold for the metallacycle and the Raman spectroscopic properties.  Solid state structural and magnetic properties for the tungsten salts were also measured and compared, in the instance of the BF4-, Br- and PF6- salts, to their molybdenum analogues.  Magnetic interactions were systematically weaker for the tungsten derivatives due to decreased spin density on the dithiolene ligand.

Structural variability of a tungsten dithiolene moiety in the homoleptic insulating salts [(Cp)2W(dmit)]+•[X]- (X = BF4-, Br-, PF6- and Au(CN)2-): A combined structural, spectroscopic and magnetic study

243rd National Meeting (2012)

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