| 邻近C-H键对中心金属原子的配位作用—[Fe(PH3)3(C8H13)]+的定域分子轨道研究 |
| COORDINATON OF NEIGHBORING C-H a BOND TO TRANSITION METAL CENTER --LOCALIZED INDO STUDY OF [Fe(PH3)3(C8H13]+ |
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| 摘要: 采用INDO方法计算了{Fe[P(OMe)3]3(C8H13)}+的简化离子[Fe(PH3)3(C8H13)]+,将正则分子轨道用Edmiston-Ruedenberg定域化方法变换为定域分子轨道,结果表明:在对应C1-H1A键的定域分子轨道中,明显包含有铁原子轨道成分(7.8%),Fe-H1A和Fe—C1键级分别为0.190和0.302。指出C1-H1A键是以一对成键σ电子配位到铁原子上的。C8H13环以包含三个碳原子的η4—共轭体系与铁原子相互作用。铁以二价(d6-Fe(Ⅱ)的形式存在于该离子中。C1-H1A键的配位满足了文献[15]提出的Fe(Ⅱ)的共价12价。 |
| 关键词: 配位键 定域分子轨道 |
| 基金项目: 高等学校科学基金 |
| Abstract: A cation [Fe(PH3)3(C8H13)]+, which was a simplified form for {Fe[P(OMe)3]3(C8H13)}+, was studied by INDO calculation. The canonical MOs (CMO) obtained from the calculation were transformed to localized MOs (LMO)by Edmiston-Ruedenberg localization method. The results show that the composition of iron atomic orbitals is obviously included in a LMO corresponding to the C1-H1A bond. The Mulliken bond orders of Fe-H1A and Fe-C: are 0.190 and 0.302, respectively. It is pointed out that the C1-H1A bond, as a two-electron donor, coordinates to iron atom through a pair of a bonding electrons. The C8H13 ring, which interacts with iroa atom, is a 4-ligand containing three π conjugated carbon atoms. The iron in this cation is in oxidation state Ⅱ (d6-Fe(Ⅱ)), and the coordination of C1-H1A bond makes the covalence of Fe(Ⅱ), VFa(Ⅱ), equal to 12. |
| Keywords: coordinate bond localized MO |
| 投稿时间：1986-04-08 |
| 摘要点击次数: 1593 |
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| 黎健,陈敏伯,徐光宪.邻近C-H键对中心金属原子的配位作用—[Fe(PH3)3(C8H13)]+的定域分子轨道研究[J].无机化学学报,1986,2(4):7-13. |
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