The bis-carbonyl Fe(II) complex trans-[Fe(PNP-iPr)(CO)2Cl]+ reacts with Zn as reducing agent under a dihydrogen atmosphere to give the Fe(II) hydride complex cis-[Fe(PNP-iPr)(CO)2H]+ in 97% isolated yield. A crucial step in this reaction seems to be the reduction of the acidic NH protons of the PNP-iPr ligand to afford H2 and the coordinatively unsaturated intermediate [Fe(PNPH-iPr)(CO)2]+ bear...

Native coordinating ligands acquired during the chemical synthesis of colloidal nanocrystals are optimized primarily for their ability to exert control over nanocrystal size, composition, morphology, and dispersibility, and not necessarily for their final application. In general, they are hydrophobic and highly insulating, and constitute a significant barrier for charge or ion transport in devi...

Treatment of hexabromoosmic acid, H2OsBr6, with 4 equiv. of tetramethylcyclopentadiene (C5Me4H2) in tert-butanol at reflux for 8 h affords the unusual salt [(C5Me4H)2OsBr]2[Os2Br8], 1, which is the bis(tetramethylcyclopentadienyl)bromoosmocinium(IV) salt of the octabromodiosmate(III) dianion. The brown color of the salt suggests that the anion adopts an eclipsed conformation (D4h symmetry) and ...

The mixed-valence triiron complexes [Fe3(CO)7-x (PPh3) x (μ-edt)2] (x = 0-2; edt = SCH2CH2S) and [Fe3(CO)5(κ2-diphosphine)(μ-edt)2] (diphosphine = dppv, dppe, dppb, dppn) have been prepared and structurally characterized. All adopt an anti arrangement of the dithiolate bridges, and PPh3 substitution occurs at the apical positions of the outer iron atoms, while the diphosphine complexes exist on...

The reactivity between a thiolate-ligated five-coordinate complex [FeII(SMe2N4(tren))]+ (1) and dioxygen is examined in order to determine if O2 activation, resembling that of the metalloenzyme cytochrome P450, can be promoted even when O2 binds cis, as opposed to trans, to a thiolate. Previous work in our group showed that [FeII(SMe2N4(tren))]+ (1) reacts readily with superoxide (O2-) in the p...

Here we report the synthesis and characterization of functional models of hydrogenases for electrocatalytic prouduction of hydrogen from weak acids. The complexes employ iron in bio-inspired coordination environments yielding catalysts that are fast and require very little electrochemical overpotential to support turnover. Progress Report Electrocatalysis by an Asymmetrically Disubstituted Diir...

Here we report the synthesis and characterization of functional models of hydrogenases for electrocatalytic prouduction of hydrogen from weak acids. The complexes employ iron in bio-inspired coordination environments yielding catalysts that are fast and require very little electrochemical overpotential to support turnover. Progress Report Electrocatalysis by an Asymmetrically Disubstituted Diir...

Reactions of Fe2(CO)6(μ-pdt) (pdt = SCH2CH2CH2S) with aminodiphosphines Ph2PN(R)PPh2 (R = allyl, (i)Pr, (i)Bu, p-tolyl, H) have been carried out under different conditions. At room temperature in MeCN with added Me3NO·2H2O, dibasal chelate complexes Fe2(CO)4{κ(2)-Ph2PN(R)PPh2}(μ-pdt) are formed, while in refluxing toluene bridge isomers Fe2(CO)4{μ-Ph2PN(R)PPh2}(μ-pdt) are the major products. Se...

The mixed-valence tr i iron complexes [Fe3(CO)7−x(PPh3)x(μ-edt)2] (x = 0−2; edt = SCH2CH2S) and [Fe3(CO)5(κ -diphosphine)(μ-edt)2] (diphosphine = dppv, dppe, dppb, dppn) have been prepared and structurally characterized. All adopt an anti arrangement of the dithiolate bridges, and PPh3 substitution occurs at the apical positions of the outer iron atoms, while the diphosphine complexes exist onl...