Coordination and conformational isomers in mononuclear iron complexes with pertinence to the [FeFe] hydrogenase active site

Coordination and conformational isomers in mononuclear iron complexes with pertinence to the [FeFe] hydrogenase active site.

A series of six mononuclear iron complexes of the type [Fe(X-bdt)(P(R)2N(Ph)2)(CO)] (P(R)2N(Ph)2 = 1,5-diaza-3,7-diphosphaoctane, bdt = benzenedithiolate with X = H, Cl2 or Me and R = Ph, Bn, Cyc or tert-Bu) was prepared. This new class of penta-coordinate iron complexes contains a free coordination site and a pendant base as essential structural features of the [FeFe]-hydrogenase active site. ...

Synthetic [FeFe] Hydrogenase Active Site Model Complexes

Introducing a dark reaction to photochemistry: photocatalytic hydrogen from [FeFe] hydrogenase active site model complexes.

The light-driven splitting of water into its constituting elements gives access to a valuable fuel from an abundant substrate, using sunlight as the only energy source. Synthetic diiron complexes as functional models of the [FeFe] hydrogenase H2ase enzyme active site have moved into the centre of focus as potentially viable catalysts for the reductive side of this process, i.e. the reduction of...

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.

Thiolate-bridged dinuclear iron(tris-carbonyl)-nickel complexes relevant to the active site of [NiFe] hydrogenase.

The reaction of NiBr(2)(EtOH)(4) with a 1:2-3 mixture of FeBr(2)(CO)(4) and Na(SPh) generated a linear trinuclear Fe-Ni-Fe cluster (CO)(3)Fe(mu-SPh)(3)Ni(mu-SPh)(3)Fe(CO)(3), 1, whereas the analogous reaction system FeBr(2)(CO)(4)/Na(S(t)Bu)/NiBr(2)(EtOH)(4) (1:2-3:1) gave rise to a linear tetranuclear Fe-Ni-Ni-Fe cluster [(CO)(3)Fe(mu-S(t)Bu)(3)Ni(mu-Br)](2), 2. By using this tetranuclear clus...