具有大位阻 N-杂环卡宾的钌-锌杂双金属配合物：合成、结构和反应性。
Heterobimetallic ruthenium-zinc complexes with bulky N-heterocyclic carbenes: syntheses, structures and reactivity.
机构信息
Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK.
出版信息
Dalton Trans. 2019 Mar 26;48(13):4176-4189. doi: 10.1039/c8dt05023f.
The ruthenium-zinc heterobimetallic complexes, [Ru(IPr)2(CO)ZnMe][BArF4] (7), [Ru(IBiox6)2(CO)(THF)ZnMe][BArF4] (12) and [Ru(IMes)'(PPh3)(CO)ZnMe] (15), have been prepared by reaction of ZnMe2 with the ruthenium N-heterocyclic carbene complexes [Ru(IPr)2(CO)H][BArF4] (1), [Ru(IBiox6)2(CO)(THF)H][BArF4] (11) and [Ru(IMes)(PPh3)(CO)HCl] respectively. 7 shows clean reactivity towards H2, yielding [Ru(IPr)2(CO)(η2-H2)(H)2ZnMe][BArF4] (8), which undergoes loss of the coordinated dihydrogen ligand upon application of vacuum to form [Ru(IPr)2(CO)(H)2ZnMe][BArF4] (9). In contrast, addition of H2 to 12 gave only a mixture of products. The tetramethyl IBiox complex [Ru(IBioxMe4)2(CO)(THF)H][BArF4] (14) failed to give any isolable Ru-Zn containing species upon reaction with ZnMe2. The cyclometallated NHC complex [Ru(IMes)'(PPh3)(CO)ZnMe] (15) added H2 across the Ru-Zn bond both in solution and in the solid-state to afford [Ru(IMes)'(PPh3)(CO)(H)2ZnMe] (17), with retention of the cyclometallation.
钌-锌杂双金属配合物[Ru(IPr)2(CO)ZnMe]BArF4、[Ru(IBiox6)2(CO)(THF)ZnMe]BArF4和Ru(IMes)’(PPh3)(CO)ZnMe是通过锌甲基与钌 N-杂环卡宾配合物[Ru(IPr)2(CO)H]BArF4、[Ru(IBiox6)2(CO)(THF)H]BArF4和[Ru(IMes)(PPh3)(CO)HCl]反应制备的。7 对 H2 表现出清洁的反应性，生成[Ru(IPr)2(CO)(η2-H2)(H)2ZnMe]BArF4，当施加真空时，该配合物失去配位的氢气配体，形成[Ru(IPr)2(CO)(H)2ZnMe]BArF4。相比之下，向 12 中添加 H2 仅得到混合物产物。与 ZnMe2 反应时，四甲基 IBiox 配合物[Ru(IBioxMe4)2(CO)(THF)H]BArF4未能生成任何可分离的含 Ru-Zn 物种。环金属化 NHC 配合物Ru(IMes)’(PPh3)(CO)ZnMe在溶液中和固态中均通过 Ru-Zn 键添加 H2，得到Ru(IMes)’(PPh3)(CO)(H)2ZnMe，同时保留了环金属化。
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