A combined experimental and computational study of the structure and reactivity of two [RuZn₂Me₂] complexes, neutral [Ru(PPh₃)(Ph₂PC₆H₄)₂(ZnMe)₂] (2) and cationic [Ru(PPh₃)₂(Ph₂PC₆H₄)(ZnMe)₂][BAr^F₄] ([BAr^F₄] = [B{3,5-(CF₃)₂C₆H₃}₄]) (3), is presented. Structural and computational analyses indicate these complexes are best formulated as containing discrete ZnMe ligands in which direct Ru–Zn bonding is complemented by weaker Zn···Zn interactions. The latter are stronger in 2, and both complexes exhibit an additional Zn···C_aryl interaction with a cyclometalated phosphine ligand, this being stronger in 3. Both 2 and 3 show diverse reactivity under thermolysis and with Lewis bases (PⁿBu₃, PCy₃, and IMes). With 3, all three Lewis bases result in the loss of [ZnMe]⁺. In contrast, 2 undergoes PPh₃ substitution with PⁿBu₃, but with IMes, loss of ZnMe₂ occurs to form [Ru(PPh₃)(C₆H₄PPh₂)(C₆H₄PPhC₆H₄Zn(IMes))H] (7). The reaction of 3 with H₂ affords the cationic trihydride complex [Ru(PPh₃)₂(ZnMe)₂(H)₃][BAr^F₄] (12). Computational analyses indicate that both 12 and 7 feature bridging hydrides that are biased toward Ru over Zn.

中文翻译：

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一对中性和阳离子杂双金属RuZn2配合物的键合和反应性

对两种 [RuZn ₂ Me ₂ ] 配合物，中性 [Ru(PPh ₃ )(Ph ₂ PC ₆ H ₄ ) ₂ (ZnMe) ₂ ] ( 2 ) 和阳离子 [Ru( PPh ₃ ) ₂ (Ph ₂ PC ₆ H ₄ )(ZnMe) ₂ ][BAr ^F ₄ ] ([BAr ^F ₄ ] = [B{3,5-(CF ₃ ) ₂ C ₆ H ₃ } ₄ ]) ( 3）， 被呈现。结构和计算分析表明，这些配合物最好配成含有离散的 ZnMe 配体，其中直接的 Ru-Zn 键合由较弱的 Zn···Zn 相互作用补充。后者在2中更强，并且两种配合物都表现出与环金属化膦配体的额外 Zn···C_芳基相互作用，这在3中更强。2和3在热解和路易斯碱（P ⁿ Bu ₃、PCy ₃和 IMes）下均表现出不同的反应性。对于3，所有三个路易斯碱都会导致 [ZnMe] ⁺的损失。相比之下，2用 P ⁿ Bu ₃进行 PPh ₃取代，但在使用 IMes 时，发生ZnMe _{2 的}损失，形成 [Ru(PPh ₃ )(C ₆ H ₄ PPh ₂ )(C ₆ H ₄ PPhC ₆ H ₄ Zn(IMes))H ] ( 7 )。3与H ₂反应得到阳离子三氢化物配合物[Ru(PPh ₃ ) ₂ (ZnMe) ₂ (H) ₃ ][BAr ^F ₄ ] ( 12 )。计算分析表明，两者图 12和7 的特征是在 Zn 上偏向 Ru 的桥接氢化物。