Determination of the Cu(III)-OH Bond Distance by Resonance Raman Spectroscopy Using a Normalized Version of Badger's Rule.
Determination of the Cu(III)-OH Bond Distance by Resonance Raman Spectroscopy Using a Normalized Version of Badger's Rule.
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DOI：
10.1021/jacs.7b00210
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发表时间：
2017-03-29
影响因子：
15
通讯作者：
Tolman WB
中科院分区：
文献类型：
--
作者：
Spaeth AD;Gagnon NL;Dhar D;Yee GM;Tolman WB
LCuOH （L = N，N′-二（2,6-二异丙基-4-R-苯基）吡啶-2,6-二羧基酰胺，R = H或NO2，或N，N′-二（2,6-二异丙基苯基）-1-甲基哌啶-2,6-二羧基酰胺）配合物中[CuOH]2+核的拉伸频率ν(Cu-O)通过共振拉曼光谱测定为~630 cm−1，并通过同位素标记进行了验证。在努力使用Badger规则来估计ν(Cu-O)对应的键距时，通过使用通过除以适当的简化质量归一化的拉伸频率，开发了该规则的修改版本。在理论和实验中发现，对于各种M-X和X-X键距离在~ 1.1-2.2 Å范围内的bbbb250个数据点，修改后的版本可以很好地拟合归一化频率与键距离（预测键距离的均方根误差为0.03 Å）。利用所得的一般方程，预测了活性[CuOH]2+核的Cu-O键距离为~1.80 Å。探讨了该方程的局限性及其在各种结构信息不可用的部分的距离预测中的应用。
The stretching frequency, ν(Cu–O), of the [CuOH]2+ core in the complexes LCuOH (L = N,N′-bis(2,6-diisopropyl-4-R-phenyl)pyridine-2,6-dicarboxamide, R = H or NO2, or N,N′-bis(2,6-diisopropylphenyl)-1-methylpiperidine-2,6-dicarboxamide) was determined to be ~630 cm−1 by resonance Raman spectroscopy and verified by isotopic labeling. In efforts to use Badger’s rule to estimate the bond distance corresponding to ν(Cu–O), a modified version of the rule was developed through use of stretching frequencies normalized by dividing by the appropriate reduced masses. The modified version was found to yield excellent fits of normalized frequencies to bond distances for >250 data points from theory and experiment for a variety of M–X and X–X bond distances in the range ~1.1–2.2 Å (root mean squared errors for the predicted bond distances of 0.03 Å). Using the resulting general equation, the Cu–O bond distance was predicted to be ~1.80 Å for the reactive [CuOH]2+ core. Limitations of the equation and its use in predictions of distances in a variety of moieties for which structural information is not available were explored.
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