Oxyl radical required for O-O bond formation in synthetic Mn-catalyst
Oxyl radical required for O-O bond formation in synthetic Mn-catalyst
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DOI：
10.1021/ic0348188
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发表时间：
2004-01-12
影响因子：
4.6
通讯作者：
Siegbahn, PEM
中科院分区：
文献类型：
--
作者：
Lundberg, M;Blomberg, MRA;Siegbahn, PEM
使用 B3LYP 泛函的 DFT 计算支持 [(terpy)(H2O)Mn-IV(mu-O)(2)Mn-III(H2O)-(terpy)](3+) (terpy=2,2':6,2"-terpyridine) 配合物作为合成 O-2 催化剂的建议。与水形成 O-O 键的计算势垒为 23 kcal/mol。在此配合物以及氧气放出配合物的模型中在 PSII 中，活性物质是 Mn-IV-氧基自由基。通过与非活性 Mn-V-氧配合物的比较，提出自由基形成实际上是 Mn 配合物中 O-2 形成活性的要求。
DFT calculations using the B3LYP functional support the suggestion that the [(terpy)(H2O)Mn-IV(mu-O)(2)Mn-III(H2O)-(terpy)](3+) (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.