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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Reduced and excited states of the intermediates (alpha-diimine)(C5R5) Rh in hydride transfer catalysis schemes: EPR and resonance Raman spectroscopy, and comparative DFT calculations of Co, Rh and Ir analogues
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Reduced and excited states of the intermediates (alpha-diimine)(C5R5) Rh in hydride transfer catalysis schemes: EPR and resonance Raman spectroscopy, and comparative DFT calculations of Co, Rh and Ir analogues

机译：氢化物转移催化方案中的中间体（α-二亚胺）（C5R5）Rh的还原态和激发态：EPR和共振拉曼光谱，以及Co，Rh和Ir类似物的比较DFT计算

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The electronic structures of the highly air-sensitive intermediates ((NN)-N-boolean AND)(C5Me5) Rh, ((NN)-N-boolean AND = 2,2'-bipyridine (bpy), 2,2'-bipyrimidine (bpym), 2,2'-bipyrazine (bpz) and 3,3'-bipyridazine (bpdz)) of hydride transfer catalysis schemes were studied through resonance Raman (rR) spectroscopy and through EPR of the reduced forms [((NN)-N-boolean AND)(C5Me5)Rh](.-). The rR results are compatible with a predominant MLCT character of the lowest excited states [((NN)-N-boolean AND)(C5Me5) Rh]*, and the EPR spectra of the reduced states reveal the presence of anion radical ligands, ((NN)-N-boolean AND)(.-), coordinated by unusually electron rich rhodium( I) centres. The experimental results, including the assignments of electronic transitions, are supported by DFT calculations for the model compounds [((NN)-N-boolean AND)(C5H5)Rh](o)/(.-), (NN)-N-boolean AND = bpy or bpym. The calculations confirm a significant but not complete mixing of metal and ligand orbitals in the lowest unoccupied MO which still retains about 3/4 pi*((NN)-N-boolean AND) character. DFT calculations on (bpy)(C5H5) M and [(bpy)(C5H5) ClM](+), M = Co, Rh, Ir, agree with the experimental results such as the differences between the homologues, especially the different LUMO characters of the precursor cations in the case of Co (--> d(M)) and Rh or Ir (--> pi*(bpy)).
机译：对空气高度敏感的中间体（（NN）-N-布尔AND）（C5Me5）Rh，（（NN）-N-布尔AND = 2,2'-联吡啶（bpy），2,2'-通过共振拉曼光谱（rR）和还原形式的EPR研究了氢化物转移催化方案的2,2'-联吡啶（bpz）和3,3'-联吡啶（bpdz）） ）-N-布尔AND）（C5Me5）Rh]（.-）。 rR结果与最低激发态[（（NN）-N-布尔AND）（C5Me5）Rh] *的主要MLCT特征兼容，并且还原态的EPR光谱揭示了阴离子自由基配体的存在，（ （NN）-N-布尔AND）（.-），由异常富电子的铑（I）中心协调。 DFT计算为模型化合物[[（（NN）-N-boolean AND]（C5H5）Rh]（o）/（.-），（NN）-N的实验结果，包括电子跃迁的分配，提供了支持。 -布尔AND = bpy或bpym。计算结果证实，在最低的未占用MO中，金属和配体轨道发生了明显但不完全的混合，该MO仍保留了大约3/4 pi *（（NN）-N-布尔AND）特征。对（bpy）（C5H5）M和[（bpy）（C5H5）ClM]（+）的DFT计算，M = Co，Rh，Ir，与实验结果吻合，例如同源物之间的差异，尤其是不同的LUMO特征Co（-> d（M））和Rh或Ir（-> pi *（bpy））的情况下，前体阳离子的含量。

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