Synthesis, Characterization, and Comparative Theoretical Investigation of Dinitrogen-Bridged Group 6-Gold Heterobimetallic Complexes.

We have prepared and characterized a series of unprecedented group 6-group 11, N-bridged, heterobimetallic [ML(η-N)(μ-η:η-N)Au(NHC)] complexes (M = Mo, W, L = diphosphine) by treatment of -[ML(N)] 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)(η-N)(μ-η:η-N)AuNHC] () and [W(depe)(η-N)(μ-η:η-N)B(CF)] (). 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 N with a d orbital of the group 6 metal overlaps in with an empty sd hybrid orbital at gold, whereas in with an sp hybrid orbital at boron. The bent N-N-LA arrangement maximizes these interactions, providing a similar level of N "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-N-[Au(NHC)] bond.