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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >The solution stability of copper(i) and silver(i) complexes with N-heterocyclic carbenes
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The solution stability of copper(i) and silver(i) complexes with N-heterocyclic carbenes

机译：铜（i）和银（i）与N-杂环卡宾络合物的溶液稳定性

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摘要

The tris-benzimidazolium cage LH_3~(3+), in MeCN solution, in the presence of OH-, forms with Cu~I and Ag~I ions complexes of formula [M~I(LH)]~(2+), in which each metal is linearly coordinated by two carbenes and one imidazolium N-H fragment remains intact. To achieve two-coordination, the two N-heterocyclic moieties of the cage make a saloon-door type motion, with a conformationally costless rotation of ca. 30° each. The two [M~I(LH)]~(2+) complexes show high thermodynamic stability and are inert with respect to metal substitution, due to the mechanical constraints imposed by the ligating framework. Complexation with Cu~I and Ag~I with the reference unidentate carbene ligand Q, derived from the benzimidazolium precursor QH~+, was studied for comparison. Both metals in MeCN form 1:1 and 1:2 complexes with the carbene ligand Q according to two stepwise equilibria. Q complexes of both metals are labile with respect to metal substitution and those of Ag~I are more stable than those of Cu ~I. A significant cooperative effect has been observed with the formation of the [Ag~IQ_2]~+ complex.
机译：在MeCN溶液中，在OH-存在下，Tris-苯并咪唑笼LH_3〜（3+）与Cu〜I和Ag〜I离子形成式[M〜I（LH）]〜（2+）的配合物，其中每种金属由两个碳烯线性地配位，并且一个咪唑NH片段保持完整。为了实现两个配位，该笼子的两个N杂环部分进行了四门轿车式运动，其构象无成本地旋转了。每个30°。由于连接框架施加的机械约束，两种[M〜I（LH）]〜（2+）配合物显示出高的热力学稳定性，并且对金属取代呈惰性。为了比较，研究了Cu〜I和Ag〜I与衍生自苯并咪唑鎓前体QH〜+的参比的未知卡宾配体Q的络合。根据两个逐步平衡，MeCN中的两种金属均与卡宾配体Q形成1：1和1：2的配合物。两种金属的Q络合物在金属取代方面不稳定，而Ag〜I的Q络合物比Cu〜I的更稳定。 [Ag〜IQ_2]〜+配合物的形成具有明显的协同作用。

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