Structural Mimics of the [Fe]-Hydrogenase: A Complete Set for Group VIII Metals

Abstract

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.

Embedding a Ruthenium-Based Structural Mimic of the [Fe]-Hydrogenase Cofactor into Papain

“…The ruthenium-based structural mimics 3 can be synthesized in two steps from the corresponding ionic carbamoyl ruthenacycles 1 by following a recently reported procedure (Scheme 2). 16 Unlike the iron analogue, thiolation of 2 requires the addition of a base. 14d The mononuclear thiolato complexes 3 could be isolated only when the pyridine ligand is substituted at the 6-position, together with a bulky thiolate (3bB); dimerization occurs otherwise (4aA, 4aB, and 4bA).…”

Group VIII carbamoyl complexes as catalysts for alkyne hydrocarboxylation and electrochemical proton reduction

“…8,9,10,11 We recently reported the synthesis and physical properties of metallacyclic carbamoyl complexes 1n as structural analogues of this cofactor for the group VIII triad, viz., iron, ruthenium and osmium (Figure 1b). 12,13,14 An interesting aspect of these complexes is that the 2mercaptopyridine ligand is hemilabile; it imparts stability to the complexes and yet is capable of decoordination at the pyridine-N. 12 This property makes the complexes potential catalysts and indeed, as we would like to report here, they are efficient catalysts for alkyne hydroxycarboxylation and electrochemical proton reduction.…”

“…The compounds 1n were synthesized according to the literature procedure. 12 Solvents that were used for reactions were distilled over the appropriate drying agents under argon before use. TLC separations were carried out on 20 x 20 cm 2 plates coated with silica gel 60 F254 from Merck.…”

Ruthenacyclic Carbamoyl Complexes: Highly Efficient Catalysts for Organosilane Hydrolysis

“…Chemicals were obtained from Sigma Aldrich and were used as received. Compounds 1 were synthesized by following a previous work reported by our group , . Solvents that were used for reactions were distilled from the appropriate drying agents under argon before use.…”