Relaxation and dissociation following photoexcitation of the (μ-N 2)[Mo(N[t-Bu]Ar)3]2 dinitrogen cleavage intermediate

Adam S. Huss, John J. Curley, Christopher C. Cummins, David A. Blank

Research output: Contribution to journalArticlepeer-review

18 Scopus citations

Abstract

Frequency resolved pump-probe spectroscopy was performed on isolated (μ-N2)[Mo(N[t-Bu]Ar)3]2 (Ar = 3,5-C 6H3Me2), an intermediate formed in the reaction of Mo(N[t-Bu]Ar)3 to bind and cleave dinitrogen. Evidence is presented for 300 fs internal conversion followed by subpicosecond vibrational cooling on the ground electronic state in competition with bond dissociation. Fast cooling following photoexcitation leads to a relatively low overall dissociation yield of 5%, in quantitative agreement with previous work [Curley, J. J.; Cooke, T. R.; Reece, S. Y.; Mueller, P.; Cummins, C. C. J. Am. Chem. Soc.2008, 130, 9394]. Coupling of vibrational modes to the excitation and internal conversion results in a nonthermal distribution of energy following conversion, and this provides sufficient bias to allow the nitrogen cleavage reaction to compete with breaking of the Mo-NN bond despite a higher energetic barrier on the ground state.

Original languageEnglish (US)
Pages (from-to)1429-1436
Number of pages8
JournalJournal of Physical Chemistry B
Volume117
Issue number5
DOIs
StatePublished - Feb 7 2013

Fingerprint Dive into the research topics of 'Relaxation and dissociation following photoexcitation of the (μ-N <sub>2</sub>)[Mo(N[t-Bu]Ar)<sub>3</sub>]<sub>2</sub> dinitrogen cleavage intermediate'. Together they form a unique fingerprint.

Cite this