Metal centers connected by conjugated bridges. A theoretical evaluation of delocalization effects
Metal centers connected by conjugated bridges. A theoretical evaluation of delocalization effects
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DOI：
10.1021/om00004a052
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发表时间：
1995-04
期刊：
影响因子：
2.8
通讯作者：
M. Sponsler
中科院分区：
文献类型：
--
作者：
M. Sponsler
(CO)2或t/2-H2PCH2PH2，X =-CHCHCHCH-、-CCCC-、p-C6H4或-NCHCHN-，m = 1或2，且n = 0、1或2（在选定的组合中）。对于L = CO，中性配合物只表现出弱的离域，但自由基阳离子和双阳离子物种表现出相对较强的Jt离域，作为测量的人口分析和有效耦合参数（Vab）的混合价阳离子。所有的桥梁研究参与n离域，与polyenediyl桥促进离域最有效。在阳离子和双阳离子配合物中，对共轭能力影响最大的桥的性质是其最高n轨道相对于金属轨道的能量，而在中性配合物中，对共轭能力影响最大的桥的性质是最低ti * 轨道的能量。对于L2 =
(CO) 2 or t/2-H2PCH2PH2, X=-CHCHCHCH-,-CCCC-, p-C6H4, or-NCHCHN-, m= 1 or 2, and n= 0, 1, or 2 (in selected combinations). For L= CO, the neutral complexes exhibit only weakdelocalization, but the radical cationic and dicationic species show relatively strong Jt delocalization, as measured by population analysis and effective coupling parameter (Vab) for the mixed-valence cations. All bridges studied participate in n delocalization, with the polyenediyl bridges promoting delocalization most effectively. Theproperty of the bridges that most strongly affects the conjugating ability in the cationic and dicationic complexes is the energy of its highest n orbital relative to themetal tia orbital, while the property that most strongly effects the conjugating ability in the neutrals is the energy of the lowest ti* orbital. For L2=