Open AccessCompeting Pathways in the Photochemistry of Ru(H)2(CO)(PPh3)3
Author(s) -
Barbara Procacci,
Simon B. Duckett,
Michael W. George,
Magnus W. D. HansonHeine,
Raphael Horvath,
Robin N. Perutz,
XueZhong Sun,
Khuong Q. Vuong,
Janet A. Welch
Publication year - 2018
Publication title -
organometallics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.231
H-Index - 172
eISSN - 1520-6041
pISSN - 0276-7333
DOI - 10.1021/acs.organomet.7b00802
Subject(s) - chemistry , photochemistry , photodissociation , spectroscopy , nuclear magnetic resonance spectroscopy , pyridine , infrared spectroscopy , reductive elimination , nanosecond , medicinal chemistry , stereochemistry , catalysis , laser , organic chemistry , quantum mechanics , optics , physics
The photochemistry of Ru(H)2(CO)(PPh3)3 (1) has been reinvestigated employing laser and conventional light sources in conjunction with NMR spectroscopy and IR spectroscopy. The sensitivity of NMR experiments was enhanced by use of p-H2-induced polarization (PHIP), and a series of unexpected reactions were observed. The photoinduced reductive elimination of H2 was demonstrated (a) via NMR spectroscopy by the observation of hyperpolarized 1 on pulsed laser photolysis in the presence of p-H2 and (b) via nanosecond time-resolved infrared (TRIR) spectroscopy studies of the transient [Ru(CO)(PPh3)3]. Elimination of H2 competes with photoinduced loss of PPh3, as demonstrated by formation of dihydrogen, triphenylarsine, and pyridine substitution products which are detected by NMR spectroscopy. The corresponding coordinatively unsaturated 16-electron intermediate [Ru(H)2(CO)(PPh3)2] exists in two isomeric forms according to TRIR spectroscopy that react with H2 and with pyridine on a nanosecond time scale. These tw...
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