Hydrogen Bonding in Crystalline Alcohol Solvates of the Platinum(II) Sulfido Complex [Pt 2 (μ‐S) 2 (PPh 3 ) 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 ] · n ROH (R = Me, Et, n Bu). 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.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)