Protonation studies of the new iron carbonyl cyanide trans-[Fe(CO)3(CN)2]2-: implications with respect to hydrogenases.
نویسندگان
چکیده
The new iron carbonyl cyanide trans-[Fe(CN)(2)(CO)(3)](2)(-), [2](2)(-), forms in high yield via photosubstitution of Fe(CO)(5) with 2 equiv of Et(4)NCN. Protonation of [2](2)(-) generated [HFe(CN)(2)(CO)(3)](-), [2H](-), the first H-Fe-CN-CO species. Further protonation gives dihydrogen. This simple system provides insights into hydrogen evolution by the hydrogenase enzymes, which also feature H-Fe-CN-CO centers.
منابع مشابه
Preparative and structural studies on the carbonyl cyanides of iron, manganese, and ruthenium: fundamentals relevant to the hydrogenases.
The reaction of cyanide, carbon monoxide, and ferrous derivatives led to the isolation of three products, trans- and cis-[Fe(CN)(4)(CO)(2)](2)(-) and [Fe(CN)(5)(CO)](3)(-), the first two of which were characterized by single-crystal X-ray diffraction. The new compounds show self-consistent IR, (13)C NMR, and mass spectroscopic properties. The reaction of trans-[Fe(CN)(4)(CO)(2)](2)(-) with Et(4...
متن کاملBimetallic carbonyl thiolates as functional models for Fe-only hydrogenases.
The anion [Fe(2)(S(2)C(3)H(6))(CN)(CO)(4)(PMe(3))](-) (2(-)) is protonated by sulfuric or toluenesulfonic acid to give HFe(2)(S(2)C(3)H(6))(CN)(CO)(4)(PMe(3)) (2H), the structure of which has the hydride bridging the Fe atoms with the PMe(3) and CN(-) trans to the same sulfur atom. (1)H, (13)C, and (31)P NMR spectroscopy revealed that HFe(2)(S(2)C(3)H(6))(CN)(CO)(4)(PMe(3)) is stereochemically ...
متن کاملThe influence of cyanide on the carbonylation of iron(II): synthesis of Fe-Sr-Cn-Co centers related to the hydrogenase active sites.
Recently iron sulfides have been proposed as being central to the emergence of life.1 For example, Huber and Wächtershäuser showed that iron sulfides catalyze carbonylation reactions leading to the formation of peptides and thioesters.2 The two best characterized Fe-S-CO enzymes (the hydrogenases) also feature cyanide, and it is likely that cyanide has a decisive stabilizing effect on the CO bi...
متن کاملHeterolytic Cleavage of Dihydrogen by an Iron(II) PNP Pincer Complex via Metal–Ligand Cooperation
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...
متن کاملDeprotonation/protonation-driven change of the σ-donor ability of a sulfur atom in iron(II) complexes with a thioamide SNS pincer type ligand.
A new iron complex with a thioamide SNS pincer type ligand, [FeBr2(κ(3)-H2L(DPM))] (κ(3)-H2L(DPM) = 2,6-bis(N-2,6-bis(diphenylmethyl)-4-isopropylphenylthioamide)pyridine), was synthesized. This complex reacts with NaH in THF to yield a unique Fe(ii) complex with two THF molecules, [Fe(THF)2(κ(3)-L(DPM))] (κ(3)-L(DPM) = 2,6-bis(N-2,6-bis(diphenylmethyl)-4-isopropylphenyliminothiolate)pyridine). ...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
عنوان ژورنال:
- Inorganic chemistry
دوره 42 17 شماره
صفحات -
تاریخ انتشار 2003