Steric Modifications Tune the Regioselectivity of the Alkane Oxidation Catalyzed by Non-Heme Iron Complexes

被引:47
作者
He, Yu [1 ]
Gorden, John D. [1 ]
Goldsmith, Christian R. [1 ]
机构
[1] Auburn Univ, Dept Chem & Biochem, Auburn, AL 36849 USA
关键词
C-H BONDS; CHIRAL METAL-COMPLEXES; MONOMERIC MN-III/II; MECHANISTIC IMPLICATIONS; OXOIRON(IV) COMPLEXES; DIOXYGEN ACTIVATION; CIS-DIHYDROXYLATION; OLEFIN OXIDATIONS; OXO; HYDROXYLATION;
D O I
10.1021/ic201695a
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Iron complexes with the tetradentate N-donor ligand N,N'-di(phenylmethyl)-N,N'-bis(2-pyridinylmethyl)-1,2-cyclohexanediamine (bbpc) are reported. Despite the benzyl groups present on the amines, the iron compounds catalyze the oxygenation of cyclohexane to an extent similar to those employing less sterically encumbered ligands. The catalytic activity is strongly dependent on the counterion, with the highest activity and the strongest preference for alkane hydroxylation correlating to the most weakly coordinating anion, SbF6-. The selectivity for the alcohol product over the ketone is amplified when acetic acid is present as an additive. When hydrocarbon substrates with both secondary and tertiary carbons are oxidized by H2O2, the catalyst directs oxidation toward the secondary carbons to a greater degree than other previously reported iron-containing homogeneous catalysts.
引用
收藏
页码:12651 / 12660
页数:10
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