Ghosh Abhik, Conradie Jeanet
Department of Chemistry, UiT The Arctic University of Norway, N-9037 Tromsø, Norway.
Department of Chemistry, University of the Free State, P.O. Box 339, Bloemfontein 9300, South Africa.
J Inorg Biochem. 2023 Jun;243:112199. doi: 10.1016/j.jinorgbio.2023.112199. Epub 2023 Mar 23.
DFT calculations with the well-tested OLYP and B3LYP* exchange-correlation functionals (along with D3 dispersion corrections and all-electron ZORA STO-TZ2P basis sets) and careful use of group theory have led to significant insights into the question of metal- versus ligand-centered redox in Co and Ni B,C-tetradehydrocorrin complexes. For the cationic complexes, both metals occur in their low-spin M(II) forms. In contrast, the charge-neutral states vary for the two metals: while the Co(I) and Co-TDC state are comparable in energy for cobalt, a low-spin Ni-TDC state is clearly preferred for nickel. The latter behavior stands in sharp contrast to other corrinoids that reportedly stabilize a Ni(I) center.
使用经过充分测试的OLYP和B3LYP*交换相关泛函进行的密度泛函理论（DFT）计算（以及D3色散校正和全电子ZORA STO-TZ2P基组），并谨慎运用群论，使得人们对钴和镍硼碳十四脱氢咕啉配合物中以金属为中心与以配体为中心的氧化还原问题有了重要的见解。对于阳离子配合物，两种金属均以其低自旋M(II)形式存在。相比之下，两种金属的电荷中性态有所不同：虽然钴的Co(I)和Co-TDC态在能量上相当，但镍明显更倾向于低自旋的Ni-TDC态。后一种行为与据报道能稳定Ni(I)中心的其他类咕啉形成了鲜明对比。
