Synthesis of bis-N-alkyl imidazolium salts and their palladium(0)(NHC)(η2-MA)2 complexes

New N-Alkyl-substituted imidazolium salts as well as a series of their corresponding [Pd(NHC)(MA)2] complexes have been obtained by three routes in good yield. The previously reported synthesis for the analogous N-aryl substituted [Pd(NHC)(MA)2] complexes has been improved. The N-alkyl-substituted [Pd(NHC)(MA)2] complexes are thermally more labile than their N-aryl counterparts. Catalytic transfer semi-hydrogenation of phenylpropyne resulted in good to excellent chemo- and stereo- selectivity conversion into (Z)-phenylpropene. The size of the alkyl substituents correlates with the rate of hydrogenation in the sense that more bulky substituents give rise to faster transfer hydrogenation rates. Copyright © 2012 John Wiley & Sons, Ltd

N-alkyl functionalised expanded ring N-heterocyclic carbene complexes of rhodium(I) and iridium(I): structural investigations and preliminary catalytic evaluation

A series of new N-alkyl functionalised 6- and 7-membered expanded ring N-heterocyclic carbene (NHC) pro-ligands 3–6 and their corresponding complexes of rhodium(I) and iridium(I), [M(NHC)(COD)Cl] 7–14 and [M(NHC)(CO)2Cl] 15–22 are described. The complexes have been characterised by 1H and 13C{1H} NMR, mass spectrometry, IR and X-ray diffraction. It is noted from X-ray diffraction studies that the N-alkyl substituents are found to orientate themselves away from the metal centre due to unfavourable steric interactions resulting in low percent buried volume (%Vbur) values in the solid state. The heterocycle ring size is also found to dictate the spatial orientation of the N-alkyl substituents in the neopentyl functionalised derivatives 10 and 14. The 7-membered derivative 14 allows for a conformational ‘twist’ of the heterocycle ring with the N-alkyl substituents adopting a mutually trans configuration with respect to each other, while the more rigid 6-membered system 10 does not allow for this conformational ‘twist’ and consequently the N-alkyl substituents adopt a mutually cis configuration. The σ-donor function of this new class of expanded ring NHC ligand has also been probed by measured IR stretching frequencies of the [M(NHC)(CO)2Cl] complexes 15–22. A preliminary catalytic survey of the hydrogenation of functionalised alkenes with molecular hydrogen under mild conditions has also been undertaken with complex 10, affording an insight into the application of large ring NHC ancillary ligands bearing N-alkyl substituents in hydrogenation transformations

Zerovalent [Pd(NHC)(Alkene)1,2] Complexes Bearing Expanded-Ring N-Heterocyclic Carbene Ligands in Transfer Hydrogenation of Alkynes

In search of more active catalysts for the transfer hydrogenation of alkynes, a series of [Pd(NHC)(MA)(1,2)] (8-14) and [Pd(NHC)(dvtms)] complexes (1-7), in which the NHC ancillary ligands are expanded-ring N-heterocyclic carbenes (erNHC's), have been prepared. These very bulky, strong a-donor ligands impart a highly constrained geometry on the complexes and in some cases enable the isolation of coordinatively and electronically unsaturated complexes (10 and 14). Their strong a-donor character is reflected in a decrease in IR stretching frequency for the C=O bond of the maleic anhydride ligands (8-14) in comparison to their five-membered counterparts. Significantly enhanced catalytic activity in the transfer hydrogenation of 1-phenyl-1-propyne is observed using [Pd(erNHC)(dvtms)] complexes (1-7) as precatalysts. The catalysts show high initial selectivity toward (Z)-alkene. However, double-bond isomerization and over-reduction to the corresponding alkane occur when all the alkyne substrate is consumed; this feature reflects the very high efficiency of these catalysts in the transfer hydrogenation of alkynes as well as alkenes