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Preparation, Characterization, Electrochemistry, and Infrared Spectroelectrochemistry of Ruthenium Nitrosyl Porphyrins Containing η 1 ‐ O ‐Bonded Axial Carboxylates
Author(s) -
Awasabisah Dennis,
Xu Nan,
Gautam Krishna P. Sharmah,
Powell Douglas R.,
Shaw Michael J.,
RichterAddo George B.
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201501115
Subject(s) - chemistry , electrochemistry , redox , porphyrin , moiety , ruthenium , carboxylate , infrared spectroscopy , cyclic voltammetry , crystal structure , medicinal chemistry , crystallography , stereochemistry , inorganic chemistry , photochemistry , electrode , organic chemistry , catalysis
The synthesis, characterization and redox behavior of eight low‐spin nitrosyl carboxylate compounds (por)Ru(NO)[η 1 ‐OC(=O)R] [por = T( p ‐OMe)PP: R = Me ( 1 ), i Pr ( 2 ), t Bu ( 3 ), p ‐C 6 H 4 NO 2 ( 4 ), Fc ( 5 ), CF 3 ( 8 ); por = TTP: R = Fc ( 6 )] and [T( p ‐OMe)PP]Ru(NO)(OC 6 HF 4 ) ( 7 ) are reported. The compounds are moderately stable in air as solids. Their IR (KBr) spectroscopic data show υ 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 CH 2 Cl 2 with NBu 4 PF 6 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.