氧化还原诱导的氢硼酸铑(3,5-二甲基吡唑基)中κ 2 -κ 3异构化化学:方锥体铑的稳定性(II)

Journal of The Chemical Society, Chemical Communications Pub Date : 1996-01-01 DOI:10.1039/CC9960002289

N. Connelly, David J. H. Emslie, Bernhard Metz, A. Orpen, M. J. Quayle

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引用次数: 24

摘要

方形平面16电子配合物[Rh(CO)(PPh3)(κ2-Tp ')]与[FeCp2][PF6]单电子氧化得到方形金字塔状的RhII配合物[Rh(CO)(PPh3)(κ3-Tp ')][PF6]，其中Tp '的第三个吡唑基在轴向位置被一个三电子双中心键n键结合(Rh - naxial比Rh - nbasal长0.13 a)。

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Redox-induced κ 2 -κ 3 isomerisation in rhodium hydrotris(3,5-dimethylpyrazolyl)borate chemistry: the stabilisation of square-pyramidal rhodium(II)

One-electron oxidation of the square-planar, 16-electron complex [Rh(CO)(PPh3)(κ2-Tp′)] with [FeCp2][PF6] gives the square-pyramidal RhII complex [Rh(CO)(PPh3)(κ3-Tp′)][PF6] in which the third pyrazolyl group of Tp′ is N-bound in the axial position by a three-electron two-centre bond (Rh–Naxial 0.13 A longer than Rh–Nbasal).

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