期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 11, 期 24, 页码 7254-7264出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200500653
关键词
density functional calculations; energy transfer; ruthenium
Photocrystallographic experiments show that laser exposure of crystals of [Ru(bpy)(2)(NO)(NO2)](PF6)(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.
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