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Photoinduced Oxygen Transfer and Double‐Linkage Isomerism in a cis ‐(NO)(NO 2 ) Transition‐Metal Complex by Photocrystallography, FT‐IR Spectroscopy and DFT Calculations
Author(s) -
Kovalevsky Andrey Yu,
King Graham,
Bagley Kimberly A.,
Coppens Philip
Publication year - 2005
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200500653
Subject(s) - isomerization , linkage isomerism , intramolecular force , chemistry , photochemistry , metastability , crystallography , metal , transition metal , spectroscopy , nitro , stereochemistry , catalysis , organic chemistry , physics , alkyl , quantum mechanics
Photocrystallographic experiments show that laser exposure of crystals of [Ru(bpy) 2 (NO)(NO 2 )](PF 6 ) 2 at 90 K produces a double isonitrosyl–nitrito linkage isomer and provide the detailed geometry of the metastable species generated. The analysis indicates that the isomerization is accomplished through an intramolecular redox reaction involving oxygen transfer from the nitro to the nitrosyl group. At 200 K only a single (nitrito) linkage isomer is formed with a U ‐shaped conformation of the nitrito group rather than the Z conformation observed at 90 K. A mechanism for the isomerization is proposed based on the crystallographic results and FTIR data collected at low temperatures during the isomerization process. The study presents the first structural evidence for double linkage isomerization in transition‐metal complexes.