Wilton-Ely James D E T, Solanki Dina, Hogarth Graeme
Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, United Kingdom.
Inorg Chem. 2006 Jun 26;45(13):5210-4. doi: 10.1021/ic060223b.
Reaction of cis-[RuCl2(dppm)2] (dppm = bis(diphenylphosphino)methane) with CS2 and NaOH yields the first ruthenium dithiocarbonate complex, [Ru(kappa2-S2C=O)(dppm)2]. Protonation with tetrafluoroboric acid affords the xanthate complex [Ru(kappa2-S2COH)(dppm)2]BF4 in a reversible manner, suggesting that this may be an intermediate in dithiocarbonate formation. [Ru(kappa2-S2C=O)(dppm)2] reacts with methyl iodide or [Me3O]BF4 to give [Ru(kappa2-S2COMe)(dppm)2]+, also obtained from the reaction of cis-[RuCl2dppm)2] with CS2 and NaOMe. Two modifications of [Ru(kappa2-S(2)C=O)(dppm)2] were examined crystallographically and the structure of [Ru(kappa2-S2COMe)(dppm)2]BF4 and a new modification of cis-[RuCl2(dppm)2] are also reported.
顺式-[RuCl₂(dppm)₂]（dppm = 双（二苯基膦基）甲烷）与CS₂和NaOH反应生成首个二硫代碳酸钌配合物[Ru(κ²-S₂C=O)(dppm)₂]。用四氟硼酸质子化以可逆方式得到黄原酸酯配合物[Ru(κ²-S₂COH)(dppm)₂]BF₄，这表明其可能是二硫代碳酸酯形成过程中的中间体。[Ru(κ²-S₂C=O)(dppm)₂]与碘甲烷或[Me₃O]BF₄反应生成[Ru(κ²-S₂COMe)(dppm)₂]⁺，该产物也可由顺式-[RuCl₂(dppm)₂]与CS₂和NaOMe反应得到。对[Ru(κ²-S(2)C=O)(dppm)₂]的两种变体进行了晶体学研究，并报道了[Ru(κ²-S₂COMe)(dppm)₂]BF₄和顺式-[RuCl₂(dppm)₂]一种新变体的结构。
