Previous work has shown that the bulky terphenyl thiols ArMe6SH (ArMe6 = -C6H3-2,6-(C6H2-2,4,6-Me3)2), ArPri4SH (ArPri4 = -C6H3-2,6-(C6H3-2,6-Pri2)2) and ArPri6SH (ArPri6 = -C6H3-2,6-(C6H2-2,4,6-Pri3)2 could stabilize monomeric divalent group 14 element metalylenes. Structurally, they displayed some of the narrowest known inter-ligand angles and an inverse correlation between terphenyl substituent size and S-M-S angle (M=Si, Ge, Sn, and Pb). Calculations suggested that this was a result of attractive dispersion force interactions between the substituents on the flanking aryl rings. In this work we investigate the effects of different substituents on the structures and properties of dithiolato- first row transition metal complexes. The synthesis, spectroscopy and structural characterization of new dithiolato- first row transition metal complexes (M = Cr, Mn, Fe, Co, Ni, Cu, Zn) are also described. We conclude that the principal forces which contribute to the bond angles observed in the dithiolato- first row transition metal complexes are intramolecular steric repulsion and dispersion between the bulky substituents across the molecules. These forces also stabilize the acute interligand angles in these complexes.

Synthetic and structural comparisons between first row transition metal dithiolato complexes and group 14 metalylenes

253rd National Meeting (2017)

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