Nonclassical oxygen atom transfer reactions of an eight-coordinate dioxomolybdenum( vi ) complex
Nonclassical oxygen atom transfer reactions of an eight-coordinate dioxomolybdenum( vi ) complex
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八配位二氧钼( vi )配合物的非经典氧原子转移反应
DOI：
10.1039/d1qi00308a
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发表时间：
2021
影响因子：
7
通讯作者：
Brown, Seth N.
中科院分区：
文献类型：
--
作者：
Ranis, Leila G.;Gianino, Jacqueline;Hoffman, Justin M.;Brown, Seth N.
二氧钼(VI)络合物MoO_2Cl2(DMF)_2与Pb(DOPOQ)_2(DOPO=2，4，6，8-tetra-tert-butyl-1，9-dioxophenoxazinate))反应得到MoO_2(DOPOQ)_2，它具有八配位结构，具有正常的钼-氧键距离和角度，但与二氧杂苯并恶嗪配体的距离延长。二氧配合物被膦脱氧生成八面体Mo(DOPOCat)2，其中辅助配体发生了还原。该化合物又与三甲胺-N-氧化物反应生成MoO2(DOPOQ)2，从而实现了磷化氢氧化的催化循环。这是一个四电子非经典氧原子转移的例子，其中既可以观察到金属络合物的氧化形式，也可以观察到还原形式。
The dioxomolybdenum(VI) complex MoO2Cl2(dmf)2 reacts with Pb(DOPOQ)2 (DOPO = 2,4,6,8-tetra-tert-butyl-1,9-dioxophenoxazinate) to give MoO2(DOPOQ)2, which has an eight-coordinate structure with normal molybdenum-oxo bond distances and angles but elongated distances to the dioxophenoxazine ligand. The dioxo complex is deoxygenated by phosphines to produce octahedral Mo(DOPOCat)2, in which reduction has taken place at the ancillary ligands. This compound in turn reacts with trimethylamine-N-oxide to regenerate MoO2(DOPOQ)2, allowing a catalytic cycle for phosphine oxidation. This represents an example of four-electron nonclassical oxygen atom transfer in which both the oxidized and reduced forms of the metal complexes can be observed.