Eight-membered-ring (diazocanylidene) N-heterocyclic carbenes (8-NHCs) are reported for the first time. The precursor salts, readily prepared by the amidine route, are converted to the free carbene by treatment with KHMDS; in general, the free NHCs can be isolated, and in one example the molecular structure was obtained. Silver complexes were prepared by direct reaction of Ag 2 O with the diazocanylidinium salts, and Rh complexes were formed by treatment of in situ formed free carbene with the appropriate Rh precursor complex. The salts and complexes were fully characterized using spectroscopic methods, including in some cases by X-ray crystallography. Key features of these new ring-expanded heterocyclic carbenes (RE-NHCs) are the extreme steric strain they impose on the metal center (they are the most sterically imposing class of NHC reported to date) and their high donor capacity, being some of the most basic NHCs currently available.

Special wettability durable coatings, with average water contact angles exceeding 140 , have been fabricated utilising functionalised hydrophobic-SiO 2 (H-SiO 2 ) particles embedded in fatty acids. The inexpensive and non-toxic H-SiO 2 particles imparted delicate lotus leaf inspired hierarchical surface nano-morphologies while the fatty acid modification afforded a suitable drop in surface energy.Comparison studies were carried out to explore the effects of fatty acid chain length and pipette as opposed to spray coating deposition methods on the coatings hydrophobicity. It was determined that the longest chain length fatty acid coatings showed enhanced hydrophobic properties due to their extended hydrophobic alkyl chain. A pipette deposited suspension containing H-SiO 2 nanoparticles and octadecanoic acid generated a coating with the most favourable average water contact and tilting angles of 142 AE 6 and 16 AE 2 respectively.

Calcium complexes supported by chiral 1,2-diamines have been shown to be efficient catalysts for the asymmetric hydroamination of amino-olefin substrates; the calcium complexes [Ca(NN(R)){N(SiMe(3))(2)}(THF)] (R = (t)Bu, (i)Pr, Ph, 4-C(6)H(4)F) give enantioselectivities of up to 26% which marks a significant increase based upon literature precedence. The structure of [Ca(NN(Ph)){N(SiMe(3))(2)}(py)] has been computed with density functional methods.

A series of calcium complexes supported by chiral bisimidazoline ligands have been studied in the catalytic intramolecular hydroamination/cyclisation of amino-olefins. The complexes [Ca(R-BIM){N(SiMe(3))(2)}(THF)] (R = 4-C(6)H(4)Me, 5a, 4-C(6)H(4)F, 5b and (t)Bu, 5c) have given competitive enantioselectivities (up to 12%) when compared to current literature studies involving calcium. Bisimidazolines offer a significant advance over similar bisoxazoline ligands, by allowing a greater structural variance through a modular synthetic pathway.

Chiral L‐valine derived diamines (I) are shown to be efficient stereodirecting ligands in the calcium‐catalyzed intramolecular hydroamination of amino‐alkenes.