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Updated: Nov 12, 2025

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Synthesis, Characterization, and Comparative Theoretical Investigation of Dinitrogen-Bridged Group 6-Gold
David Specklin1, Anaïs Coffinet1, Laure Vendier1
1LCC-CNRS, Université de Toulouse, CNRS, UPS, 205 route de Narbonne, BP44099, F-31077 Toulouse cedex 4, France.
Abstract:
We have prepared and characterized a series of unprecedented group 6-group 11, N2-bridged, heterobimetallic [ML4(η1-N2)(μ-η1:η1-N2)Au(NHC)]+ complexes (M = Mo, W, L2 = diphosphine) by treatment of trans-[ML4(N2)2] with a cationic gold(I) complex [Au(NHC)]+. The adducts are very labile in solution and in the solid, especially in the case of molybdenum, and decomposition pathways are likely initiated by electron transfers from the zerovalent group 6 atom to gold. Spectroscopic and structural parameters point to the fact that the gold adducts are very similar to Lewis pairs formed out of strong main-group Lewis acids (LA) and low-valent, end-on dinitrogen complexes, with a bent M-N-N-Au motif. To verify how far the analogy goes, we computed the electronic structures of [W(depe)2(η1-N2)(μ-η1:η1-N2)AuNHC]+ (10+) and [W(depe)2(η1-N2)(μ-η1:η1-N2)B(C6F5)3] (11). A careful analysis of the frontier orbitals of both compounds shows that a filled orbital resulting from the combination of the π* orbital of the bridging N2 with a d orbital of the group 6 metal overlaps in 10+ with an empty sd hybrid orbital at gold, whereas in 11 with an sp3 hybrid orbital at boron. The bent N-N-LA arrangement maximizes these interactions, providing a similar level of N2 "push-pull" activation in the two compounds. In the gold case, the HOMO-2 orbital is further delocalized to the empty carbenic p orbital, and an NBO analysis suggests an important electrostatic component in the μ-N2-[Au(NHC)]+ bond.
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