Mechanistic study of the photofragmentation of the clusters [Os3(CO)10(diene)] (diene = cis- 1,3-butadiene, 1,3-cyclohexadiene): Direct observation of the open-triangle primary photoproduct with nanosecond time-resolved infrared and UV-Vis spectroscopy

Maarten J. Bakker, Frank W. Vergeer, František Hartl, Omar S. Jina, Xue Zhong Sun, Michael W. George

Research output: Journal PublicationArticlepeer-review

8 Citations (Scopus)

Abstract

The photochemistry of the clusters [Os3(CO)10(diene)] (diene = cis-1,3-butadiene, 1,3-cyclohexadiene) was studied in detail. Upon near-UV irradiation photofragmentation occurs to give mononuclear [Os(CO)3(diene)]. The second fragmentation product [Os2(CO)7] was trapped by reaction with CO, or with alkenes at low temperatures, to produce the dinuclear complexes [Os2(CO)7(L)2] (L = CO, ethene, 1-octene). The fragmentation was studied further with nanosecond time-resolved UV-Vis and IR spectroscopy and was found to proceed via the initial formation of a triosmium photoproduct with a lifetime of about 100 ns in hexane. From the spectroscopic data we infer that this intermediate has a coordinatively unsaturated open-triangle structure with two bridging carbonyl groups, one bridging the split (CO)4Os-Os(CO)2(diene) bond. (C) 2000 Elsevier Science S.A.

Original languageEnglish
Pages (from-to)597-603
Number of pages7
JournalInorganica Chimica Acta
Volume300-302
DOIs
Publication statusPublished - 30 Apr 2000
Externally publishedYes

Keywords

  • Diene complexes
  • Osmium complexes
  • Photochemistry
  • Triosmium complexes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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