Lundberg Marcus, Blomberg Margareta R A, Siegbahn Per E M
Department of Physics, Stockholm University, AlbaNova University Center, Stockholm Center for Physics, Astronomy and Biotechnology, SE-106 91 Stockholm, Sweden.
Inorg Chem. 2004 Jan 12;43(1):264-74. doi: 10.1021/ic0348188.
DFT calculations using the B3LYP functional support the suggestion that the (terpy)(H(2)O)Mn(IV)(micro-O)(2)Mn(III)(H(2)O)(terpy) (terpy=2,2':6,2' '-terpyridine) complex functions as a synthetic O(2) catalyst. The calculated barrier for O-O bond formation with water is 23 kcal/mol. In this complex, as well as in models of the oxygen evolving complex in PSII, the active species is a Mn(IV)-oxyl radical. From comparisons with inactive Mn(V)-oxo complexes, it is proposed that radical formation is actually a requirement for O(2) formation activity in Mn-complexes.
使用B3LYP泛函的密度泛函理论（DFT）计算结果支持了(terpy)(H₂O)Mn(IV)(μ-O)₂Mn(III)(H₂O)(terpy)（terpy = 2,2':6,2''-三联吡啶）配合物作为合成O₂催化剂的观点。计算得出的与水形成O-O键的能垒为23千卡/摩尔。在该配合物以及光合系统II中放氧复合体的模型中，活性物种是Mn(IV)-氧自由基。通过与无活性的Mn(V)-氧代配合物进行比较，有人提出自由基的形成实际上是Mn配合物中O₂形成活性的必要条件。
