32073-70-4Relevant academic research and scientific papers
Synthesis, Characterization, and Comparative Theoretical Investigation of Dinitrogen-Bridged Group 6-Gold Heterobimetallic Complexes
Specklin, David,Coffinet, Ana?s,Vendier, Laure,Del Rosal, Iker,Dinoi, Chiara,Simonneau, Antoine
supporting information, p. 5545 - 5562 (2021/04/09)
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]+ (10W+) and [W(depe)2(η1-N2)(μ-η1:η1-N2)B(C6F5)3] (11W). 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 10W+ with an empty sd hybrid orbital at gold, whereas in 11W 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.
