title: Molecular spectroscopy of uranium(IV) bis(ketimido) complexes. rare observation of resonance-enhanced raman scattering from organoactinide complexes and evidence for broken-symmetry excited states.
abstract: Electronic absorption and resonance-enhanced Raman spectra for ketimido (azavinylidene) complexes of tetravalent uranium, (C(5)Me(5))(2)U[-N=C(Ph)(R)](2) (R = Ph, Me, and CH(2)Ph), have been recorded. The absorption spectra exhibit four broad bands between 13 000 and 24 000 cm(-1). The highest-energy band is assigned to the ketimido-localized p( perpendicular)(N)-->pi(N=C) transition based on comparison to the spectra of (C(5)H(5))(2)Zr[-N=CPh(2)](2) and (C(5)Me(5))(2)Th[-N=CPh(2)](2). Upon excitation into any of these four absorption bands, the (C(5)Me(5))(2)U[-N=C(Ph)(R)](2) complexes exhibit resonance enhancement for several Raman bands attributable to vibrations of the ketimido ligands. Raman bands for both the symmetric and nominally asymmetric N=C stretching bands are resonantly enhanced upon excitation into the p( perpendicular)(N)-->pi(N=C) absorption bands, indicating that the excited state is localized on a single ketimido ligand. Raman excitation profiles for (C(5)Me(5))(2)U[-N=CPh(2)](2) confirm that at least one of the lower-energy electronic absorption bands (E(max) approximately 16300 cm(-1)) is a charge-transfer transition between the U(IV) center and the ketimido ligand(s). The observations of both charge-transfer transitions and resonance enhancement of Raman vibrational bands are exceedingly rare for tetravalent actinide complexes and reflect the strong bonding interactions between the uranium 5f/6d orbitals and those on the ketimido ligands.
authors.affiliation: Chemistry Division and the Glenn T. Seaborg Institute for Transactinium Science, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA.
authors.forename: Ryan E
authors.initials: RE
authors.lastname: Da Re
authors.forename: Kimberly C
authors.initials: KC
authors.lastname: Jantunen
authors.forename: Jeffrey T
authors.initials: JT
authors.lastname: Golden
authors.forename: Jaqueline L
authors.initials: JL
authors.lastname: Kiplinger
authors.forename: David E
authors.initials: DE
authors.lastname: Morris