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Synthesis and Reactivity of the Ruthenium(II) Dithiocarbonate Complex [Ru(κ2-S2CO)(dppm)2] (dppm = Bis(diphenylphosphino)methane)

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posted on 26.06.2006 by James D. E. T. Wilton-Ely, Dina Solanki, Graeme Hogarth
Reaction of cis-[RuCl2(dppm)2] (dppm = bis(diphenylphosphino)methane) with CS2 and NaOH yields the first ruthenium dithiocarbonate complex, [Ru(κ2-S2CO)(dppm)2]. Protonation with tetrafluoroboric acid affords the xanthate complex [Ru(κ2-S2COH)(dppm)2]BF4 in a reversible manner, suggesting that this may be an intermediate in dithiocarbonate formation. [Ru(κ2-S2CO)(dppm)2] reacts with methyl iodide or [Me3O]BF4 to give [Ru(κ2-S2COMe)(dppm)2]+, also obtained from the reaction of cis-[RuCl2(dppm)2] with CS2 and NaOMe. Two modifications of [Ru(κ2-S2CO)(dppm)2] were examined crystallographically and the structure of [Ru(κ2-S2COMe)(dppm)2]BF4 and a new modification of cis-[RuCl2(dppm)2] are also reported.

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