title: On the mechanism of imine elimination from Fischer tungsten carbene complexes.
abstract: (Aminoferrocenyl)(ferrocenyl)carbene(pentacarbonyl)tungsten(0) (CO)5W=C(NHFc)Fc (W(CO) 5 ( E -2)) is synthesized by nucleophilic substitution of the ethoxy group of (CO)5W=C(OEt)Fc (M(CO) 5 (1 (Et) )) by ferrocenyl amide Fc-NH(-) (Fc = ferrocenyl). W(CO) 5 ( E -2) thermally and photochemically eliminates bulky E-1,2-diferrocenylimine ( E -3) via a formal 1,2-H shift from the N to the carbene C atom. Kinetic and mechanistic studies to the formation of imine E -3 are performed by NMR, IR and UV-vis spectroscopy and liquid injection field desorption ionization (LIFDI) mass spectrometry as well as by trapping experiments for low-coordinate tungsten complexes with triphenylphosphane. W(CO) 5 ( E -2) decays thermally in a first-order rate-law with a Gibbs free energy of activation of ΔG (‡) 298K = 112 kJ mol(-1). Three proposed mechanistic pathways are taken into account and supported by detailed (time-dependent) densitiy functional theory [(TD)-DFT] calculations. The preferred pathway is initiated by an irreversible CO dissociation, followed by an oxidative addition/pseudorotation/reductive elimination pathway with short-lived, elusive seven-coordinate hydrido tungsten(II) intermediates cis (N,H)-W(CO) 4 (H)( Z -15) and cis (C,H)-W(CO) 4 (H)( Z -15).
authors: Institute of Inorganic and Analytical Chemistry, Johannes Gutenberg-University, Duesbergweg 10-14, 55128 Mainz, Germany.
authors: Philipp
authors: P
authors: Veit
authors: Institute of Inorganic and Analytical Chemistry, Johannes Gutenberg-University, Duesbergweg 10-14, 55128 Mainz, Germany.
authors: Christoph
authors: C
authors: Förster
authors: Institute of Inorganic and Analytical Chemistry, Johannes Gutenberg-University, Duesbergweg 10-14, 55128 Mainz, Germany.
authors: Katja
authors: K
authors: Heinze
keywords: carbene complexes; ferrocene; imine; mechanism; tungsten