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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >UV-visible spectroscopy of macrocyclic alkyl, nitrosyl and halide complexes of cobalt and rhodium. Experiment and calculation
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UV-visible spectroscopy of macrocyclic alkyl, nitrosyl and halide complexes of cobalt and rhodium. Experiment and calculation

机译：钴和铑的大环烷基，亚硝酰基和卤化物配合物的紫外可见光谱。实验与计算

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摘要

Transition metal complexes (NH3)(5)CoX2+ (X = CH3, Cl) and L(H2O)MX2+, where M = Rh or Co, X = CH3, NO, or Cl, and L is a macrocyclic N-4 ligand are examined by both experiment and computation to better understand their electronic spectra and associated photochemistry. Specifically, irradiation into weak visible bands of nitrosyl and alkyl complexes (NH3)(5)CoCH32+ and L(H2O)(MX2+)-X-III (X = CH3 or NO) leads to photohomolysis that generates the divalent metal complex and (CH3)-C-center dot or (NO)-N-center dot, respectively. On the other hand, when X = halide or NO2, visible light photolysis leads to dissociation of X-and/or cis/trans isomerization. Computations show that visible bands for alkyl and nitrosyl complexes involve transitions from M-X bonding orbitals and/or metal d orbitals to M-X antibonding orbitals. In contrast, complexes with X = Cl or NO2 exhibit only d-d bands in the visible, so that homolytic cleavage of the M-X bond requires UV photolysis. UV-Vis spectra are not significantly dependent on the structure of the equatorial ligands, as shown by similar spectral features for (NH3)(5)CoCH32+ and L-1(H2O)CoCH32+.
机译：过渡金属配合物（NH3）（5）CoX2 +（X = CH3，Cl）和L（H2O）MX2 +，其中M = Rh或Co，X = CH3，NO或Cl，L为大环N-4配体通过实验和计算进行检查，以更好地了解其电子光谱和相关的光化学。具体来说，辐射到亚硝酰基和烷基络合物（NH3）（5）CoCH32 +和L（H2O）（MX2 +）-X-III（X = CH3或NO）的可见可见光带中会导致光均溶，生成二价金属络合物和（CH3 ）-C中心点或（NO）-N中心点。另一方面，当X ＝卤化物或NO 2时，可见光光解导致X-和/或顺式/反式异构化的解离。计算表明，烷基和亚硝酰基配合物的可见带涉及从M-X键合轨道和/或金属d轨道到M-X反键合轨道的过渡。相反，具有X = Cl或NO2的配合物在可见光中仅显示d-d带，因此M-X键的均相裂解需要进行UV光解。如（NH3）（5）CoCH32 +和L-1（H2O）CoCH32 +的相似光谱特征所示，UV-Vis光谱不明显依赖于赤道配体的结构。

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