Preparation, Characterization, Electrochemistry, and Infrared Spectroelectrochemistry of Ruthenium Nitrosyl Porphyrins Containing η1-O-Bonded Axial Carboxylates

被引：10
作者：
Awasabisah, Dennis [1 ]
Xu, Nan [1 ,2 ]
Gautam, Krishna P. Sharmah [3 ]
Powell, Douglas R. [1 ]
Shaw, Michael J. [3 ]
Richter-Addo, George B. [1 ]
机构：
[1] Univ Oklahoma, Dept Chem & Biochem, 101 Stephenson Pkwy, Norman, OK 73019 USA
[2] Penn State Altoona, Div Math & Nat Sci, 3000 Ivyside Pk, Altoona, PA 16601 USA
[3] So Illinois Univ, Dept Chem, Edwardsville, IL 62025 USA
来源：
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2016年 / 04期
基金：
美国国家科学基金会;
关键词：
Redox chemistry; Spectroelectrochemistry; Cyclic voltammetry; Porphyrinoids; Ruthenium; Nitrosyl ligands; NITRIC-OXIDE; CRYSTAL-STRUCTURE; REFLECTANCE SPECTROELECTROCHEMISTRY; REDOX PROPERTIES; FERROCENE; COMPLEXES; LIGANDS; ANTIMALARIAL; CATALASE; IRON;
D O I：
10.1002/ejic.201501115
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The synthesis, characterization and redox behavior of eight low-spin nitrosyl carboxylate compounds (por)Ru(NO){eta(1)-OC(=O)R] [por = T(p-OMe)PP: R = Me (1), iPr (2), tBu (3), p-C6H4NO2 (4), Fc (5), CF3 (8); por = TTP: R = Fc (6)] and [T(p-OMe)PP[Ru(NO)(OC6HF4) (7) are reported. The compounds are moderately stable in air as solids. Their IR (KBr) spectroscopic data show upsilon(NO).s in the 1839-1861 cm(-1) range. The X-ray crystal structures of compounds 1, 2, 5-7, and 8 have been determined, and reveal linear RuNO linkages for these formally {RuNO}(6) complexes. The redox behavior of the compounds at a Pt working electrode were studied in CH2Cl2 with NBu4PF6 as supporting electrolyte. The compounds display reversible first oxidations. IR spectroelectrochemistry of compounds 1-4, 7 and 8 revealed porphyrin-centered oxidations, whereas the ferrocenylcarboxylate compounds revealed first oxidations at the ferrocenyl moiety followed by second oxidations at the porphyrin macrocycles. Reductions of these compounds are accompanied by loss of the axial ligands.
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页码：509 / 518
页数：10
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