Insertion Reactions of [M(SR)3(PMe2Ph)2] with CS2 (M = Ru, Os; R = C6F4H-4, C6F5). X-ray Structures of [Ru(S2CSC6F4H-4)2(PMe2Ph)2], trans-Thiolates [M(SR)2(S2CSR)(PMe2Ph)2] (M = Ru; R = C6F5 and M = Os; R = C6F4H-4), and trans-Thiolate−Phosphine [Os(SC6F5)2(S2CSC6F5)(PMe2Ph)2]

Reactions of [M(SR)3(PMe2Ph)2] (M = Ru, Os; R = C6F4H-4, C6F5) with CS2 in acetone afford [Ru(S2CSR)2(PMe2Ph)2] (R = C6F4H-4, 1; C6F5, 3) and trans-thiolates [Ru(SR)2(S2CSR)(PMe2Ph)2] (R = C6F4H-4, 2; C6F5, 4) or the
isomers trans-thiolates [Os(SR)2(S2CSR)(PMe2Ph)2] (R = C6F4H-4, 5; C6F5, 7) and trans-thiolate−phosphine [Os(SR)2(S2CSR)(PMe2Ph)2] (R = C6F4H-4, 6; C6F5, 8) through processes involving CS2 insertion into M−SR bonds.
The ruthenium(III) complexes [Ru(SR)3(PMe2Ph)2] react with CS2 to give the diamagnetic thiolate−thioxanthato
ruthenium(II) and the paramagnetic ruthenium(III) complexes while osmium(III) complexes [Os(SR)3(PMe2Ph)2] react
to give the paramagnetic thiolate−thioxanthato osmium(III) isomers. The single-crystal X-ray diffraction studies of
1, 4, 5, and 8 show distorted octahedral structures. 31P {1H} and 19F NMR studies show that the solution structures
of 1 and 3 are consistent with the solid-state structure of 1.

在与二硫化碳(CS2)的丙酮溶液中，配合物[M(SR)3(PMe2Ph)2]（M为Ru或Os；R为C6F4H-4或C6F5）可生成[Ru(S2CSR)2(PMe2Ph)2]（R为C6F4H-4，1；C6F5，3）以及反式硫醇配体[ Ru(SR)2(S2CSR)(PMe2Ph)2]（R为C6F4H-4，2；C6F5，4）或其同分异构体反式硫醇配体[Os(SR)2(S2CSR)(PMe2Ph)2]（R为C6F4H-4，5；C6F5，7）以及反式硫醇配体-膦[Os(SR)2(S2CSR)(PMe2Ph)2]（R为C6F4H-4，6；C6F5，8），通过CS2插入至M-SR键中的过程实现。钌(III)配合物[Ru(SR)3(PMe2Ph)2]与CS2反应生成抗磁性硫醇配体-硫氧杂蒽钌(II)和顺磁性钌(III)配合物，而钇(III)配合物[Os(SR)3(PMe2Ph)2]则反应生成顺磁性硫醇配体-硫氧杂蒽钇(III)同分异构体。对于1、4、5和8的单晶X射线衍射研究表明，这些物质呈现畸变的八面体结构。31P{1H}和19F核磁共振研究表明，1和3的溶液结构与其固态结构1相一致。