Effects of Methyl Substitution in Ruthenium Tris(2-pyridylmethyl)amine Photocaging Groups for Nitriles

被引：25

作者：

Arora, Karan ^{[1
]}

White, Jessica K. ^{[2
]}

Sharma, Rajgopal ^{[1
]}

Mazumder, Shivnath ^{[1
]}

Martin, Philip D. ^{[1
]}

Schlegel, H. Bernhard ^{[1
]}

Turro, Claudia ^{[2
]}

Kodanko, Jeremy J. ^{[1
,3
]}

机构：

[1] Wayne State Univ, Dept Chem, 5101 Cass Ave, Detroit, MI 48202 USA

[2] Ohio State Univ, Dept Chem & Biochem, Columbus, OH 43210 USA

[3] Barbara Ann Karmanos Canc Inst, Detroit, MI 48201 USA

来源：

INORGANIC CHEMISTRY | 2016年 / 55卷 / 14期

基金：

美国国家科学基金会; 美国国家卫生研究院;

关键词：

COUPLED ELECTRON-TRANSFER; LIGAND-EXCHANGE; HYDROCARBON OXYGENATION; PYRIDYLAMINE COMPLEXES; EXCITATION-ENERGIES; ORGANIC-COMPOUNDS; RU(II) COMPLEXES; WATER OXIDATION; DENSITY; MONONUCLEAR;

D O I：

10.1021/acs.inorgchem.6b00650

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Four complexes of the general formula [Ru(L)(CH3CN)(2)](PF6)(2), [L = TPA (5), MeTPA (6), Me(2)TPA (7), and Me(3)TPA (8)] [TPA = tris[(pyridin-2-yl)methyl]amine, where methyl groups were introduced consecutively onto the 6-position of py donors of TPA, were prepared and characterized by various spectroscopic techniques and mass spectrometry. While 5 and 8 were isolated as single stereoisomers, 6 and 7 were isolated as mixtures of stereoisomers in 2:1 and 1.5:1 ratios, respectively. Steric effects on ground state stability and thermal and photochemical reactivities were studied for all four complexes using H-1 NMR and electronic absorption spectroscopies and computational studies. These studies confirmed that the addition of steric bulk accelerates photochemical and thermal nitrile release.

引用

页码：6968 / 6979

页数：12

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