Carbenes. Pincers, chelates, and abnormal binding modes
Carbenes. Pincers, chelates, and abnormal binding modes
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DOI：
10.1351/pac200375040435
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发表时间：
2003-04-01
影响因子：
1.8
通讯作者：
Crabtree, RH
中科院分区：
文献类型：
--
作者：
Crabtree, RH
Pd、Rh和Ir的卡宾络合物的合成途径包括双配位CH活化、金属化和CH活化。可能会发生通过咪唑C5的异常结合，离子配对会强烈影响C2与C5的结合。在金属化之前，事先通过吡啶N结合配体是不必要的。计算方法被广泛使用，例如，比较咪唑中的N和C结合。讨论了金属酶中组氨酸与C结合的可能性。
Routes to pincer and chelate carbene complexes of Pd, Rh, and Ir include double geminal CH activation, metallation, and CH activation. Abnormal binding via imidazole C5 can occur, and ion pairing can strongly influence C2 vs. C5 binding. Prior ligand binding via pyridine N before metallation is not essential. Computational methods are used extensively, for example, to compare N vs. C binding in imidazole. The possibility of C binding by histidine in metalloenzymes is discussed.