Reactivity of Cationic Triruthenium Carbonyl Clusters: From Pyrimidinium Ligands to N-Heterocyclic Carbenes
Reactivity of Cationic Triruthenium Carbonyl Clusters: From Pyrimidinium Ligands to N-Heterocyclic Carbenes
复制标题
阳离子三钌羰基簇的反应性：从嘧啶配体到 N-杂环卡宾
DOI：
10.1021/om101130g
复制
发表时间：
2011
期刊：
影响因子：
2.8
通讯作者：
Vanessa Pruneda
中科院分区：
文献类型：
--
作者：
Javier A. Cabeza;I. D. Rı́o;E. Pérez;Vanessa Pruneda
[Ru3(CO)12] 与嘧啶 (Hpym) 反应生成异构环金属化衍生物 [Ru3(μ-H)(μ-κ2N1,C6-pym)(CO)10] (1) 和 [Ru3(μ-H)(μ-κ2N1,C2-pym)(CO)10] (2)，经 [Me3O][BF4] 处理后得到相应的N-甲基嘧啶衍生物 [Ru3(μ-H)(μ-κ2N1,C6-pymMe)(CO)10][BF4] (3[BF4]) 和 [Ru3(μ-H)(μ-κ2N1,C2-pymMe)(CO)10][BF4] (4[BF4])。 4[BF4] 与 K-Selectride 的反应产生两种中性三核产物的可分离混合物，[Ru3(μ-H){μ-κ2N1,C2-(6-HpymMe)}(CO)9] (5) 和 [Ru3(μ-H){μ-κ2N1,C2-(4-HpymMe)}(CO)9] (6)，其由亲核攻击产生4+配体C6和C4碳原子上的氢化物。这种阳离子复合物可以被还原为短命自由基物种 4•，它通过在两个此类自由基的配体之间形成分子间 CC 键而自发二聚。三种六核衍生物，[Ru6(μ-H)2{μ6-κ4N1,N1',C2,C2'-(4,6'-bipymMe2)}(CO)18]（异构体7和8）和[Ru6(μ-H)2{μ6-κ4N1,N1',C2,C2'-(4,4'-bipymMe2)}(CO)18]（是...
The reaction of [Ru3(CO)12] with pyrimidine (Hpym) leads to the isomeric cyclometalated derivatives [Ru3(μ-H)(μ-κ2N1,C6-pym)(CO)10] (1) and [Ru3(μ-H)(μ-κ2N1,C2-pym)(CO)10] (2), which have been treated with [Me3O][BF4] to give the corresponding N-methylpyrimidinium derivatives [Ru3(μ-H)(μ-κ2N1,C6-pymMe)(CO)10][BF4] (3[BF4]) and [Ru3(μ-H)(μ-κ2N1,C2-pymMe)(CO)10][BF4] (4[BF4]). The reaction of 4[BF4] with K-Selectride renders a separable mixture of two neutral trinuclear products, [Ru3(μ-H){μ-κ2N1,C2-(6-HpymMe)}(CO)9] (5) and [Ru3(μ-H){μ-κ2N1,C2-(4-HpymMe)}(CO)9] (6), which arise from the nucleophilic attack of a hydride at the ligand C6 and C4 carbon atoms of 4+. This cationic complex can be reduced to the short-lived radical species 4•, which spontaneously dimerizes by forming an intermolecular C−C bond between the ligands of two such radicals. Three hexanuclear derivatives, [Ru6(μ-H)2{μ6-κ4N1,N1′,C2,C2′-(4,6′-bipymMe2)}(CO)18] (isomers 7 and 8) and [Ru6(μ-H)2{μ6-κ4N1,N1′,C2,C2′-(4,4′-bipymMe2)}(CO)18] (is...