Redox-switched oxidation of dihydrogen using a non-innocent ligand
Redox-switched oxidation of dihydrogen using a non-innocent ligand
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DOI：
10.1021/ja076801k
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发表时间：
2008-01-23
影响因子：
15
通讯作者：
Rauchfuss, Thomas B.
中科院分区：
文献类型：
--
作者：
Ringenberg, Mark R.;Kokatam, Swarna Latha;Rauchfuss, Thomas B.
发现含有Cp* Ir（（t）BA（F）Ph））（1）类型的非无辜配体的有机络合物以氧化还原可切换的方式活化H-2，其中H2（t）BA（F）Ph是2-（2-三氟甲基）苯胺基-4，6-二叔丁酚。16 e（-）配合物1在氧化前对H-2、CO以及常规碱性底物呈惰性。用1当量的Ag+氧化16-电子1导致配体中心氧化，得到[1]（+）的盐，其通过晶体学、EPR和元素分析表征。[1](+）在H-2和空间位阻碱2，6-（Bu-t）（2）C5 H3 N存在下通过金属和二氢的一级反应途径还原为1。化合物[1]（+）与MeCN形成加合物，抑制催化作用。通过电化学方法建立了H_2的催化氧化与单价阳离子的关系。
Organometallic complexes containing non-innocent ligands of the type Cp*lr((t)BA(F)Ph))(1), where H2(t)BA(F)Ph is 2-(2-trifluoromethyl)anilino-4,6-di-tert-butophenol, were found to activate H-2 in a redox-switchable manner. The 16e(-) complex 1 was inert with respect to H-2, CO, as well as conventional basic substrates until oxidation. Oxidation of 16-electron 1 with 1 equiv of Ag+ resulted in ligand-centered oxidation affording salts of [1](+), which were characterized by crystallographically, EPR, and elemental analyses. [1](+) was reduced to 1 in the presence of H-2 and the sterically hindered base, 2,6-(Bu-t)(2)C5H3N, via a pathway that is first-order in both metal and dihydrogen. Compound [1](+) forms adducts; with MeCN, which inhibits catalysis. The catalytic oxidation of H2 was established by electrochemical methods to be associated with the monocation.