Issue 47, 2014

Picosecond time-resolved infrared spectroscopy of rhodium and iridium azides

Abstract

Picosecond time-resolved infrared spectroscopy was used to elucidate early photochemical processes in the diazido complexes M(Cp*)(N3)2(PPh3), M = Rh (1), Ir (2), using 266 nm and 400 nm excitation in THF, CH2Cl2, MeCN and toluene solutions. The time-resolved data have been interpreted with the aid of DFT calculations on vibrational spectra of the singlet ground states and triplet excited states and their rotamers. While the yields of phototransformations via N2 loss are low in both complexes, 2 cleaves a N3 ligand under 266 nm excitation. The molecular structure of 1 is also reported as determined by single crystal X-ray diffraction.

Graphical abstract: Picosecond time-resolved infrared spectroscopy of rhodium and iridium azides

Supplementary files

Article information

Article type
Paper
Submitted
10 Jul 2014
Accepted
14 Aug 2014
First published
15 Aug 2014

Dalton Trans., 2014,43, 17694-17702

Author version available

Picosecond time-resolved infrared spectroscopy of rhodium and iridium azides

P. Portius, A. J. H. M. Meijer, M. Towrie, B. F. Crozier and I. Schiager, Dalton Trans., 2014, 43, 17694 DOI: 10.1039/C4DT02097A

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