title: Unusual, bifurcated photoreactivity of a rhenium(I) carbonyl complex of triethynylphosphine.
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.
authors.affiliation: Department of Chemistry, University of Wyoming, P.O. Box 3838, Laramie, Wyoming 82071, USA.
authors.forename: Sean E
authors.initials: SE
authors.lastname: Hightower
authors.forename: Robert C
authors.initials: RC
authors.lastname: Corcoran
authors.forename: B Patrick
authors.initials: BP
authors.lastname: Sullivan