In this work, we employ density functional theory to assign vibrational signatures of [FeFe]-hydrogenase intermediates to molecular structures. For this purpose, we perform an exhaustive analysis of structures and harmonic vibrations of a series of CN and CO containing model clusters of the [FeFe]-hydrogenase enzyme active site considering also different charges, counterions, and solvents. The ...

Most reported examples of transition metal-mediated pericyclic reactions have been shown to proceed by nonpericyclic mechanisms. However, the conversion of Fe(CO)(4)-cyclobutenes to Fe(CO)(3)-butadienes and CO is thought to proceed through a mechanism involving an electrocyclic ring-opening step. We have examined this and possible alternative mechanisms for the parent Fe(CO)(4)-cyclobutene comp...

The first examples of boryl substituted aluminylene and gallylene complexes, [(DAB)B(THF)Al{Fe(CO)3(μ-CO)}]2 and [(DAB)BGa{μ-Fe(CO)4}]2 (DAB = {(C6H3Pri2-2,6)NCH}2) have been prepared by reduction of MX2(THF){B(DAB)} (M = Al or Ga, X = Cl or Br) with K2[Fe(CO)4]. Spectroscopic and crystallographic analyses of the compounds show them to be structurally distinct dimers, the latter of which posses...

Treatment of anhydrous FeX2 (X = Cl, Br) with 1 equiv. of the asymmetric chiral PNP pincer ligands PNP-R,TAD (R = iPr, tBu) with an R,R-TADDOL (TAD) moiety afforded complexes of the general formula [Fe(PNP)X2]. In the solid state these complexes adopt a tetrahedral geometry with the PNP ligand coordinated in κ(2)P,N-fashion, as shown by X-ray crystallography and Mössbauer spectroscopy. Magnetiz...

The HypC and HypD maturases are required for the biosynthesis of the Fe(CN)(2)CO cofactor in the large subunit of [NiFe]-hydrogenases. Using infrared spectroscopy we demonstrate that an anaerobically purified, Strep-tagged HypCD complex from Escherichia coli exhibits absorption bands characteristic of diatomic CO and CN(-) ligands as well as CO(2). Metal and sulphide analyses revealed that alon...

This paper intends to review the state-of-the-art in the field of ferromagnetic shape memory alloys different than Ni–Mn–Ga, developed in the ast years. It starts with the effects of additions of different fourth elements to Ni–Mn–Ga and continues with the review of other Heusler (or B2) i-based and Co-based alloy systems, like Ni–Mn–X, Ni–Fe–Ga, Co–Ni–Al and Co–Ni–Ga alloys. Finally, ferromagn...

Reaction of LSn(NMe(2))Fe(CO)(4) (L = CH{(CMe)(2,6-iPr(2)C(6)H(3)N)}(2)) with H(2)O gave the first example of a monomeric tin(ii) hydroxide complex LSn(OH)Fe(CO)(4).

Electron-rich polyisocyano derivatives Fe(2)(S(2)C(n)H(2n)(CO)(6-x)(CNMe)(x) (x approximately 4) undergo oxidatively induced (FeCp(2)(+)) reaction with additional CNMe to give [Fe(2)(SR)(2)(CNMe)(7)](PF(6))(2), a new class of iron thiolates. Crystallographic characterization established that the 34 e(-) dinuclear core resembles the oxidized (H(2)-binding) form of the active sites of the Fe-only...