title: Rotameric transformations in the photochemistry of TpM(CO)2(η(3)-C3H4R), where Tp = tris(pyrazolyl)borate, M = Mo or W, and R = H or Me.
abstract: Low energy photolysis of TpM(CO)2(η(3)-C3H4R), where Tp = tris(pyrazolyl)borate, M = Mo or W, and R = 2-H or 2-Me in PVC matrices at 85 K results in exo/gauche isomerism of the allyl ligand. This transformation comes in contrast to the behaviour observed in cyclopentadienyl analogues which undergo exo/endo isomerism. DFT computations reveal an η(3) → η(1)* → η(3) mechanism for the allyl rotameric interconversion where the η(1)*-allyl intermediate is generated upon MLCT excitation.
authors.affiliation: Department of Chemistry, University of Idaho, 875 Perimeter Dr, MS 2343, Moscow, ID 83843-2343, USA. bitterte@uidaho.edu.
authors.forename: Wyatt A
authors.initials: WA
authors.lastname: Thornley
authors.forename: Thomas E
authors.initials: TE
authors.lastname: Bitterwolf