Control of .eta.2-coordination vs. carbon-hydrogen bond activation by rhodium: the role of aromatic resonance energies
Control of .eta.2-coordination vs. carbon-hydrogen bond activation by rhodium: the role of aromatic resonance energies
复制标题
铑对 eta2 配位与碳氢键活化的控制：芳香族共振能量的作用
DOI：
--
复制
发表时间：
1993
期刊：
影响因子：
--
通讯作者：
R. Perutz
中科院分区：
文献类型：
--
作者：
R. Chin;Lingzhen Dong;S. Duckett;M. Partridge;W. Jones;R. Perutz
The reactions of a series of fused polycyclic arenes with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})(Ph)H and (C{sub 5}H{sub 5})Rh(PMe{sub 3})-(Ph)H have been examined, and the thermodynamic preferences for {eta}{sup 2}-arene coordination vs C-H bond activation have been determined. While naphthalene, perylene, and triphenylene give equilibrium mixtures of both C-H activation and {eta}{sup 2}-complexes, phenanthrene, anthracene, 2-methoxynaphthalene,2,6-dimethoxynaphthalene, pyrene, and fluoranthene give only {eta}{sup 2}-complexes (C{sub 5}Me{sub 5} complexes). Naphthalene and several of the polycyclic aromatics are found to give bis-{eta}{sup 2}-complexes upon extended reaction. Electron-withdrawing groups as in p-C{sub 6}H{sub 4}(CF{sub 3}){sub 2} and m-C{sub 6}H{sub 4}(CF{sub 3}){sub 2} are also found to promote {eta}{sup 2}-coordination in monocyclic arenes (C{sub 5}H{sub 5} complexes). A C{sub 5}H{sub 5} ligand favors {eta}{sup 2}-coordination compared to a C{sub 5}Me{sub 5} ligand, as does rhodium compared to iridium. The effects of resonance, specifically the differences in the Huckel energies of the {eta}{sup 2}-bound vs free ligand, are believed to control the C-H activation/{eta}{sup 2}-coordination equilibria in polycyclic systems. The perylene complex (C{sub 5}Me{sub 5})Rh(PMe{sub 3})({eta}{sup 2}-perylene) has been found to crystallize in monoclinic space group C2/c, with a = 32.927(10)A, b = 10.125(2) A, c = 18.129(8) A, {beta} = 100.30(3){degree}, V = 5946.5(6.3) A{sup 3},more » and Z = 8. 29 refs., 3 figs., 6 tabs.« less
The reactions of a series of fused polycyclic arenes with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})(Ph)H and (C{sub 5}H{sub 5})Rh(PMe{sub 3})-(Ph)H have been examined, and the thermodynamic preferences for {eta}{sup 2}-arene coordination vs C-H bond activation have been determined. While naphthalene, perylene, and triphenylene give equilibrium mixtures of both C-H activation and {eta}{sup 2}-complexes, phenanthrene, anthracene, 2-methoxynaphthalene,2,6-dimethoxynaphthalene, pyrene, and fluoranthene give only {eta}{sup 2}-complexes (C{sub 5}Me{sub 5} complexes). Naphthalene and several of the polycyclic aromatics are found to give bis-{eta}{sup 2}-complexes upon extended reaction. Electron-withdrawing groups as in p-C{sub 6}H{sub 4}(CF{sub 3}){sub 2} and m-C{sub 6}H{sub 4}(CF{sub 3}){sub 2} are also found to promote {eta}{sup 2}-coordination in monocyclic arenes (C{sub 5}H{sub 5} complexes). A C{sub 5}H{sub 5} ligand favors {eta}{sup 2}-coordination compared to a C{sub 5}Me{sub 5} ligand, as does rhodium compared to iridium. The effects of resonance, specifically the differences in the Huckel energies of the {eta}{sup 2}-bound vs free ligand, are believed to control the C-H activation/{eta}{sup 2}-coordination equilibria in polycyclic systems. The perylene complex (C{sub 5}Me{sub 5})Rh(PMe{sub 3})({eta}{sup 2}-perylene) has been found to crystallize in monoclinic space group C2/c, with a = 32.927(10)A, b = 10.125(2) A, c = 18.129(8) A, {beta} = 100.30(3){degree}, V = 5946.5(6.3) A{sup 3},more » and Z = 8. 29 refs., 3 figs., 6 tabs.« less