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Photolysis of Isoelectronic Ruthenium Nitrosyl and Diazonium Complexes in Frozen PVC Matrices: Retention of Dinitrogen on Ruthenium Following Photochemical Phenyl Radical Loss
Author(s) -
Thornley Wyatt A.,
Bitterwolf Thomas E.
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.201501100
Subject(s) - chemistry , ruthenium , photodissociation , photochemistry , linkage isomerism , decomposition , homolysis , ligand (biochemistry) , electron transfer , radical ion , metal , radical , catalysis , organic chemistry , ion , biochemistry , receptor
Photolysis of RuCl 3 (η 1 ‐NO)(PPh 3 ) 2 in poly(vinyl chloride) (PVC) matrices at 85 K results in reversible linkage isomerism of the nitrosyl ligand to form the isonitrosyl complex RuCl 3 (η 1 ‐ON)(PPh 3 ) 2 . Metal‐to‐ligand charge‐transfer (MLCT) excitation of the isoelectronic phenylazo complex, RuCl 3 (η 1 ‐N 2 Ph)(PPh 3 ) 2 , has previously been shown to result in generation of the phenyl radical, presumably through decomposition a photogenerated diazenyl radical. Examination of this photolysis in a PVC matrix at cryogenic temperatures has permitted direct observation of an isotopically sensitive product band that may be assigned to a 17‐electron ruthenium dinitrogen species, suggesting that this photochemical decomposition does not proceed through formation of a diazenyl intermediate but through homolytic cleavage of the parent diazonium complex to give the phenyl radical and the 17‐electron RuCl 3 (η 1 ‐N 2 )(PPh 3 ) 2 .