Spectroscopic and computational studies of a series of high-spin Ni(II) thiolate complexes.

ABSTRACT: The electronic structures of a series of high-spin Ni(II)-thiolate complexes of the form [PhTt(tBu)]Ni(SR) (R = CPh(3), 2; C(6)F(5), 3; C(6)H(5), 4; PhTt(tBu) = phenyltris((tert-butylthio)methyl)borate) have been characterized using a combined spectroscopic and computational approach. Resonance Raman (rR) spectroscopic data reveal that the nu(Ni-SR) vibrational feature occurs between 404 and 436 cm(-1) in these species. The corresponding rR excitation profiles display a striking de-enhancement behavior because of interference effects involving energetically proximate electronic excited states. These data were analyzed in the framework of time-dependent Heller theory to obtain quantitative insight into excited state nuclear distortions. The electronic absorption and magnetic circular dichro

SUBMITTER: Van Heuvelen KM 

PROVIDER: S-EPMC2914102 | biostudies-literature | 2010 Jul

REPOSITORIES: biostudies-literature