Cabeza Javier A, del Río Ignacio, Martínez-Méndez Lorena, Miguel Daniel
Departamento de Química Orgánica e Inorgánica, Instituto de Química Organometálica Enrique Moles, Universidad de Oviedo, 33071 Oviedo, Spain.
Chemistry. 2006 Feb 1;12(5):1529-38. doi: 10.1002/chem.200500813.
The treatment of [Ru3(CO)12] with 6,6'-dimethyl-2,2'-bipyridine (Me2bipy) or 2,9-dimethyl-1,10-phenanthroline (Me2phen) in THF at reflux temperature gives the trinuclear dihydride complexes [Ru3(mu-H)2(mu3-L1)(CO)8] (L1 = HCbipyMe 1 a, HCphenMe 1 b), which result from the activation of two C-H bonds of a methyl group. The hexa-, hepta-, and pentanuclear derivatives [Ru6(mu3-H)(mu5-L2)(mu-CO)3(CO)13] (L2 = CbipyMe 2 a, CphenMe 2 b), [Ru7(mu3-H)(mu5-L2)(mu-CO)2(CO)16] (L2 = CbipyMe 3 a, CphenMe 3 b), and [Ru5(mu-H)(mu5-C)(mu-L3)(CO)13] (L3 = bipyMe 4 a, phenMe 4 b) can also be obtained by treating 1 a and 1 b with [Ru3(CO)12]. Compounds 2 a and 2 b have a basal edge-bridged square-pyramidal metallic skeleton with a carbyne-type C atom capping the four Ru atoms of the pyramid base. The structures of 3 a and 3 b are similar to those of 2 a and 2 b, respectively, but an additional Ru atom now caps a triangular face of the square-pyramidal fragment of the metallic skeleton. The most interesting feature of 2 a, 2 b, 3 a, and 3 b is that their carbyne-type C atoms were originally bound to three hydrogen atoms in Me2bipy or Me2phen and, therefore, they arise from the unprecedented activation of all three C-H bonds of C-bound methyl groups. The pentanuclear compounds 4 a and 4 b contain a carbide ligand surrounded by five Ru atoms in a distorted trigonal-bipyramidal environment. They are the products of a series of processes that includes the activation of all bonds (three C-H and one C-C) of organic methyl groups, and are the first examples of complexes having carbide ligands that arise from C-bonded methyl groups. The alkenyl derivatives [Ru5(mu5-C)(mu-p-MeC6H4CHCHphenMe)(CO)13] (5 b), [Ru5(mu-H)(mu5-C)(mu-p-MeC6H4CHCHphenMe)(p-tolC2)(CO)12] (6 b), and [Ru5(mu-H)(mu5-C)(mu-PhCHCHphenMe)(PhC2)(CO)12] (7 b) have been obtained by treating 4 b with p-tolyl- and phenylacetylene, respectively. Their heterocyclic ligands contain an alkenyl fragment in the position that was originally occupied by a methyl group. Therefore, these complexes are the result of the formal substitution of an alkenyl group for a methyl group of 2,9-dimethyl-1,10- phenanthroline.
在回流温度下，于四氢呋喃（THF）中用6,6'-二甲基-2,2'-联吡啶（Me2bipy）或2,9-二甲基-1,10-菲咯啉（Me2phen）处理[Ru3(CO)12]，可得到三核二氢配合物[Ru3(μ-H)2(μ3-L1)(CO)8]（L1 = HCbipyMe 1 a，HCphenMe 1 b），这是由甲基的两个C-H键活化产生的。六核、七核和五核衍生物[Ru6(μ3-H)(μ5-L2)(μ-CO)3(CO)13]（L2 = CbipyMe 2 a，CphenMe 2 b）、[Ru7(μ3-H)(μ5-L2)(μ-CO)2(CO)16]（L2 = CbipyMe 3 a，CphenMe 3 b）和[Ru5(μ-H)(μ5-C)(μ-L3)(CO)13]（L3 = bipyMe 4 a，phenMe 4 b）也可通过用[Ru3(CO)12]处理1 a和1 b得到。化合物2 a和2 b具有一个底面边缘桥连的正方锥型金属骨架，一个卡拜型C原子覆盖在锥底的四个Ru原子上。3 a和3 b的结构分别与2 a和2 b相似，但现在有一个额外的Ru原子覆盖在金属骨架正方锥型片段的一个三角形面上。2 a、2 b、3 a和3 b最有趣的特征是它们的卡拜型C原子最初与Me2bipy或Me2phen中的三个氢原子相连，因此，它们源自C-键合甲基的所有三个C-H键前所未有的活化。五核化合物4 a和4 b在扭曲的三角双锥环境中含有一个被五个Ru原子包围的碳化物配体。它们是一系列过程的产物，这些过程包括有机甲基的所有键（三个C-H和一个C-C）的活化，并且是具有源自C-键合甲基的碳化物配体的配合物的首个例子。烯基衍生物[Ru5(μ5-C)(μ-p-MeC6H4CHCHphenMe)(CO)13]（5 b）、[Ru5(μ-H)(μ5-C)(μ-p-MeC6H4CHCHphenMe)(p-tolC2)(CO)12]（6 b）和[Ru5(μ-H)(μ5-C)(μ-PhCHCHphenMe)(PhC2)(CO)12]（7 b）分别通过用对甲苯基乙炔和苯乙炔处理4 b得到。它们的杂环配体在原本被甲基占据的位置含有一个烯基片段。因此，这些配合物是2,9-二甲基-1,10-菲咯啉的一个甲基被一个烯基正式取代的结果。
