Complex Formation and Rearrangement Reactions of the Phosphine Hydride Anions [OsH₃(PPh₃)₃]^- and [IrH₂(PPh₃)₃]^-

[OsH4(PPh3)3] (1) reacts with KH in THF in the presence of 18-crown-6 to form [K(THF)(18-crown-6)][OsH3(PPh3)3] (2), characterized by NMR spectroscopy and X-ray crystallography; cation−anion contact is achieved through three Os−H···K moieties. In contrast, [IrH3(PPh3)3] (6) reacts with KH and 18-crown-6 in THF with redistribution of ligands to produce the known bis-phosphine complex [K(18-crown-6)][IrH4(PPh3)2] (7). This reaction has been followed by NMR spectroscopy, and [IrH2(PPh3)3]- has been identified as a likely intermediate. K[OsH3(PPh3)3] (3) reacts with Bun3SnCl to form the tin-osmium complex [OsH3(SnBun3)(PPh3)3] (8), characterized by NMR spectroscopy and X-ray crystallography. The molecule contains a seven-coordinate osmium center, which can be described approximately as a distorted fac-[OsH3(PPh3)] arrangement, with the SnBun3 moiety capping the OsH3 face.配合物1：[OsH₄(三苯基膦(PPh₃))₃]在18-冠-6存在下，于四氢呋喃(THF)中与氢化钾(KH)反应，生成配合物2：[K(THF)(18-冠-6)][OsH₃(三苯基膦)₃]，该产物通过核磁共振(NMR)光谱与X射线晶体学完成表征；阴阳离子间通过三处Os−H···K相互作用实现接触。与之相反，配合物6：[IrH₃(三苯基膦)₃]在四氢呋喃中与氢化钾及18-冠-6反应，伴随配体重分布过程，生成已知双膦配合物7：[K(18-冠-6)][IrH₄(三苯基膦)₂]。该反应通过核磁共振光谱进行追踪，中间体被推定是[IrH₂(三苯基膦)₃]⁻。配合物3：K[OsH₃(三苯基膦)₃]与氯化三正丁基锡(Bun3SnCl)反应，生成锡-锇配合物8：[OsH₃(SnBun3)(三苯基膦)₃]，该产物通过核磁共振光谱与X射线晶体学完成表征。该配合物分子含有一个七配位锇中心，其结构可近似描述为畸变的面式(fac)-[OsH₃(三苯基膦)]构型，其中SnBun3基团覆盖于OsH₃面之上。