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Unusual, bifurcated photoreactivity of a rhenium(I) carbonyl complex of triethynylphosphine.

Authors
  • Hightower, Sean E
  • Corcoran, Robert C
  • Sullivan, B Patrick
Type
Published Article
Journal
Inorganic Chemistry
Publisher
American Chemical Society (ACS)
Publication Date
Dec 26, 2005
Volume
44
Issue
26
Pages
9601–9603
Identifiers
PMID: 16363818
Source
Medline
License
Unknown

Abstract

Preparations of the first metal complexes of triethynylphosphine (TEP) are described. They are of the type fac-Re(bpy)(CO)(3)(TEP)(+) (1) and cis,trans-[Re(bpy)(CO)(2)(TEP)L](n)(+) (CH(3)CN, n = 1, complex 2; Cl, n = 0, complex 3), where bpy is 2,2'-bipyridine. Complex 1 displays unusual photochemical behavior compared to analogous fac-[Re(bpy)(CO)(3)(PR(3))](+) complexes in that it emits from a state that has pi-pi* character but undergoes competitive photosubstitution of both TEP and CO. Density functional theory (DFT)/time-dependent DFT calculations predict that the lowest emitting state should, in fact, have pi-pi* character.

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