Borane-Protected Cyanides as Surrogates of H-Bonded Cyanides in [FeFe]-Hydrogenase Active Site Models

Synthetic [FeFe] Hydrogenase Active Site Model Complexes

Detoxication of Aromatic Cyanides

The toxicity, physiologic effects, and antidotes are the points emphasized in the existing literature on the cyanides; Giacosa and Baumann alone have been interested in their fate in the body. Reports are unanimous that the aliphatic cyanides split off hydrocyanic acid, and that toxicity is directly proportional to the rate at which this splitting occurs, while an increase in the excretion of t...

Directing protonation in [FeFe] hydrogenase active site models by modifications in their second coordination sphere.

Subtle changes in the second coordination sphere of [Cl(2)bdtFe(2)(CO)(4)(Ph(2)P-CH(2)-X-CH(2)-PPh(2))] (bdt = benzene-1,2-dithiolate, X = NCH(3), NCH(2)CF(3), CH(2)) that do not influence the electronic character of the Fe(2) center can however direct protonation to three different sites: the N in the bis-phosphane, the Fe-Fe bond or the bdt-S.

Resin-bound models of the [FeFe]-hydrogenase enzyme active site and studies of their reactivity.

The immobilization of synthetic analogues of the [FeFe]-hydrogenase, [FeFe]H(2)ase, enzyme active site on polyethyleneglycol-rich polystyrene beads is described. Using the reactivity of the amine termini of the PEG chains with carboxylates incorporated into (mu-SRS)[Fe(CO)(3)](2) or (mu-SR)(2)[Fe(CO)(3)](2) derivative, nu(CO)IR signatures can be used to interrogate the structure and properties ...

Hydrogen Production Catalyzed by Bidirectional, Biomimetic Models of the [FeFe]-Hydrogenase Active Site

Active site mimics of [FeFe]-hydrogenase are shown to be bidirectional catalysts, producing H2 upon treatment with protons and reducing equivalents. This reactivity complements the previously reported oxidation of H2 by these same catalysts in the presence of oxidants. The complex Fe2(adtBn)(CO)3(dppv)(PFc*Et2 ) ([1]0; adtBn = (SCH2)2NBn, dppv = cis-1,2-bis(diphenylphosphino)ethylene, PFc*Et2 =...