New complexes containing N-heterocyclic vinylene-stabilized [BH] fragments were prepared, and surprisingly it was found that the precursor N-heterocyclic olefins (NHOs) could promote the mild (room temperature) catalytic hydroborylation of ketones and aldehydes. This finding represents an important addition to the burgeoning field of non-metal mediated catalysis.

New N‐heterocyclic olefins (NHOs) are described with functionalization on the ligand heterocyclic backbone and terminal alkylidene positions. Various PdII–NHO complexes have been formed and their use as pre‐catalysts in Buchwald–Hartwig aminations was explored. The most active system for catalytic C−N bond formation between hindered arylamine and arylhalide substrates was accessed by combining a backbone methylated NHO with [Pd(cinnamyl)Cl]2 in the presence of NaOtBu as a base. In these active systems evidence suggests that catalysis is mediated by colloidal palladium metal, highlighting a different coordination ability of NHOs in comparison with commonly used N‐heterocyclic carbene co‐ligands.

Anionic N-heterocyclic olefins (aNHOs) are suited well for the stabilization of low-coordinate inorganic complexes, due to their steric tunability and strong σand π-electron donating abilities. In this study, the new two-coordinate zinc complex ( Me IPrCH) 2 Zn ( Me IPrCH = [(MeCNDipp) 2 CCH] − , Dipp = 2,6diisopropylphenyl) is shown to participate in a broad range of metathesis reactions with main group element-based halides and hydrides. In the case of the group 14 halides, Cl 2 E•dioxane (E = Ge and Sn), transmetalation occurs to form dinuclear propellane-shaped cations, [( Me IPrCHE) 2 (μ-Cl)] + , while the aNHO-capped phosphine ligand Me IPrCH-PPh 2 is obtained when ( Me IPrCH) 2 Zn is combined with ClPPh 2 . Lastly, ZnH 2 elimination drives transmetalation between ( Me IPrCH) 2 Zn and hydroboranes and hydroalumanes, leading to Lewis acidic aNHO-supported -boryl and -alane products.

The synthesis of new trialkylaluminum adducts with N‐heterocyclic olefin (NHO) ligands is described. These well‐defined complexes can catalyze the polymerization of various Michael‐type monomers, such as 2‐vinylpyridine, methylacrylate, and dimethylacrylamide.

Dedicated to Prof. Cameron Jones on the Occasion of his 60 th Birthday.The synthesis of anionic N-heterocyclic olefin (aNHO)-supported Group 4 metal complexes was achieved by salt metathesis reactions between a lithiated aNHO and Group 4 metal tetrahalides. A ligand-activated bis-aNHO Zr(II) complex was also obtained and structurally characterized.Given our recent report of the lithiated aNHO ( Me IPrCH)Li ( Me IPrCH = [(MeCNDipp) 2 C=CH] À ; Dipp = 2,6-iPr 2 C 6 H 3 ), and its [a] I.