ic050266c_si_001.cif (42.26 kB)
Dynamics of a cis-Dihydrogen/Hydride Complex of Iridium
dataset
posted on 2005-09-05, 00:00 authored by H. V. Nanishankar, Saikat Dutta, Munirathinam Nethaji, Balaji R. JagirdarInsertion of CS2 into one of the Ir−H bonds of [Ir(H)5(PCy3)2] takes place to afford the dihydrido dithioformate
complex cis-[Ir(H)2(η2-S2CH)(PCy3)2] accompanied by the elimination of H2. Protonation of the dithioformate complex
using HBF4·Et2O gives cis-[Ir(H)(η2-H2)(η2-S2CH)(PCy3)2][BF4] wherein the H atom undergoes site exchange between
the dihydrogen and the hydride ligands. The dynamics was found to be so extremely rapid with respect to the
NMR time scale that the barrier to exchange could not be measured. Partial deuteration of the hydride ligands
resulted in a J(H,D) of 6.5 and 7.7 Hz for the H2D and the HD2 isotopomers of cis-[Ir(H)(η2-H2)(η2-S2CH)(PCy3)2][BF4], respectively. The H−H distance (dHH) for this complex has been calculated to be 1.05 Å, which can be
categorized under the class of elongated dihydrogen complexes. The cis-[Ir(H)(η2-H2)(η2-S2CH)(PCy3)2][BF4] complex
undergoes substitution of the bound H2 moiety with CH3CN and CO resulting in new hydride derivatives, cis-[Ir(H)(L)(η2-S2CH)(PCy3)2][BF4] (L = CH3CN, CO). Reaction of cis-[Ir(H)2(η2-S2CH)(PCy3)2] with electrophilic reagents
such as MeOTf and Me3SiOTf afforded a new hydride aquo complex cis-[Ir(H)(H2O)(η2-S2CH)(PCy3)2][OTf] via the
elimination of CH4 and Me3SiH, respectively, followed by the binding of a water molecule (present in trace quantities
in the solvent) to the iridium center. The X-ray crystal structures of cis-[Ir(H)2(η2-S2CH)(PCy3)2] and cis-[Ir(H)(H2O)(η2-S2CH)(PCy3)2][OTf] have been determined.
