Hydrogen Bonding in Crystalline Alcohol Solvates of the Platinum(II) Sulfido Complex [Pt2(μ‐S)2(PPh3)4]

Suspension of [Pt 2 (μ-S) 2 (PPh 3 ) 4 ] in lower alcohols results in recrystallisation, forming yellow to yellow-orange microcrystals of the solvates [Pt 2 (μ-S) 2 (PPh 3 ) 4 ]·nROH (R = Me, Et, nBu). The di-ethanol solvate was characterised by means of a single-crystal X-ray diffraction study and 1 H NMR spectroscopy. The structure consists of an ethanol molecule hydrogen-bonded in an asymmetric bifurcated fashion to the {Pt 2 S 2 } group, with the second, disordered ethanol molecule involved in a cooperative hydrogen-bonding interaction with the oxygen of the first ethanol. Thermogravimetric analysis shows that the alcohol is relatively easily lost, regenerating orange, unsolvated [Pt 2 (μ-S) 2 (PPh 3 ) 4 ]. [Pt 2 (μ-S) 2 (PPh 3 ) 4 ] readily dissolves in hexafluoro-2-propanol, yielding yellow crystals of [Pt 2 (μ-S) 2 (PPh 3 ) 4 ]· 6 (CF 3 ) 2 CHOH on evaporation. Characterisation by X-ray diffraction shows that the structure contains a [Pt 2 (μ-S) 2 (PPh 3 ) 4 ] hydrogen-bonded to a single (CF 3 ) 2 CHOH molecule, with the additional (CF 3 ) 2 CHOH molecules forming a discrete hydrogen-bonded pentameric cluster in the crystal.