Reactions of Singlet Oxygen with Organometallic Compounds. 4. Photooxidation of Cationic Iridium(I) and Rhodium(I) Complexes with Weakly Bonded Ligands.
Reactions of Singlet Oxygen with Organometallic Compounds. 4. Photooxidation of Cationic Iridium(I) and Rhodium(I) Complexes with Weakly Bonded Ligands.
复制标题
单线态氧与有机金属化合物的反应。
DOI：
10.1021/ic960056n
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发表时间：
1996
影响因子：
4.6
通讯作者：
C. Foote
中科院分区：
文献类型：
--
作者：
M. Selke;L. Rosenberg;J. Salvo;C. Foote
[M（CO）S（PPh（3））（2）]（+）（M = Ir，Rh; S = CH（3）CN）型阳离子配合物与单线态氧反应生成相应的过氧配合物[M（CO）S（PPh（3））（2）（O（2））]（+）。溶剂分子保持与氧加合物中的金属配位。新型阳离子铱-过氧络合物在室温下稳定，而铑-过氧络合物仅在0 ℃以下稳定。与单线态氧的配合物的物理和化学相互作用的速率常数略小于那些相关的中性配合物。在添加烯烃（四甲基乙烯或1-辛烯）的过氧配合物，既没有氧化的烯烃，也没有取代的乙腈配体观察。1-辛烯在阳离子铑（I）配合物作用下异构化主要得到2-和3-辛烯。已经具有配位二烯配体（[Ir（COD）（PPh（3））（2）]（+））的阳离子铱配合物不与单线态氧反应或猝灭单线态氧。
Cationic complexes of the type [M(CO)S(PPh(3))(2)](+) (M = Ir, Rh; S = CH(3)CN) react with singlet oxygen to form the corresponding peroxo complexes [M(CO)S(PPh(3))(2)(O(2))](+). The solvent molecule remains coordinated to the metal in the oxygen adducts. The novel cationic iridium-peroxo complex is stable at room temperature, while the rhodium-peroxo complex is only stable below 0 degrees C. Rate constants for physical and chemical interaction of the complexes with singlet oxygen are somewhat smaller than those for related neutral complexes. Upon addition of alkenes (tetramethylethylene or 1-octene) to the peroxo complexes, neither oxidation of the olefins nor substitution of the acetonitrile ligand was observed. 1-Octene was isomerized to give mostly 2- and 3-octene by the cationic rhodium(I) complex. A cationic iridium complex which already possesses a coordinated diene ligand ([Ir(COD)(PPh(3))(2)](+)) did not react with or quench singlet oxygen.