Competition between agostic WCH2+ and HWCH+: A joint experimental and theoretical study

Abstract

Interaction of lead atom with atmospheric hydroxyl radical. An ab initio and density functional theory study of the resulting complexes PbOH and HPbO Probes of spin conservation in heavy metal reactions: Experimental and theoretical studies of the reactions of Re + with H 2 , D 2 , and HD

The most reactive third-row transition metal: Guided ion beam and theoretical studies of the activation of methane by Ir+

“…This implicitly assumes that the spin-orbit corrections largely cancel. This assumption has been tested for the W + + CH 4 system where Maitre and coworkers had explicitly calculated spin-orbit interactions ranging from 0.06 to 0.29 eV for several tungsten-containing molecular ions compared to the 0.51 eV value for atomic W + [54]. These results indicate that spin-orbit effects are likely to reduce the theoretical bond energies in the present work but by less than the 0.64 eV value associated with the atomic ion.…”

Infrared spectroscopy of organometallic ions in the gas phase: From model to real world complexes

“…In these high-level quantum chemical calculations, it was assumed that the [M,C,2H] þ dehydrogenation product was a methylene complex with a C 2v structure (Irikura & Goddard, 1994). In fact, a more detailed study in the case of M = W suggested that there are two alternative structures: a carbene-like WCH 2 þ , but with a Cs structure resulting from an agostic distortion, and a hydridomethylidynetungsten HWCH þ one (Simon et al, 2001). These results were supported by two recent studies by Armentrout and co-workers of the reactivity of W þ and Ir þ towards methane (Armentrout, Shin, & Liyanage, 2006;Li, Zhang, & Armentrout, 2006).…”

Photofragment spectroscopy of covalently bound transition metal complexes: a window into C–H and C–C bond activation by transition metal ions

“…The photodissociation spectrum of TaCH þ 2 is unstructured and shows an onset at 249 nm, giving D o 0 (Ta þ -CH 2 ) 480 AE 5 kJ mol À1 . The only other experimental determination of this value is based on the [63]. They observe loss of H atom starting at 2.5 AE 0.1 eV and calculate that the metallocarbene and HWCH þ isomers are nearly isoenergetic.…”