A set of structural mimics of the [Fe]-hydrogenase active site comprising all the group VIII metals, viz., [M(2-NHC(O)CHN)(CO)(2-S-CHN)], has been synthesized. They exist as a mixture of isomers in solution, and the relative stability of the isomers depends on the nature of the metal and the substituent at the 6-position of the pyridine ligand.

We describe the synthesis of the ruthenacyclic carbamoyl complexes [Ru(2-NHC(O)CHNMe)(CO)( o,o-Me-CHS)(L)] (L = HO or MeCN), which have a labile water or acetonitrile ligand at their sixth coordination sites. Steric bulk around the ruthenium center is essential in preventing isomerization and dimerization, and embedding within papain can be achieved via coordination of its sole free cysteine residue. The observed chemistry parallels that of the natural [Fe]-hydrogenase.

The ruthenacyclic carbamoyl complexes [RuX{2-NHC(O)C 5 H 3 NR}(CO) 2 (NCMe)] (R = H and Me; X = Br and SC 6 H 3o,o-Me 2 ) are excellent catalysts for the hydrolysis of organosilanes, particularly towards primary silanes, generating hydrogen [a]

No abstract

No abstract