ArticleInorganic chemistry2014
Borane-protected cyanides as surrogates of H-bonded cyanides in [FeFe]-hydrogenase active site models.
Article in Inorganic chemistry, 2014. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 6 papers.
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Who cites it
6 citing papers in PubMed.
- Facile electrocatalytic proton reduction by a [Fe-Fe]-hydrogenase bio-inspired synthetic model bearing a terminal CNChemical science · 2024Article
- Geometrical influence on the non-biomimetic heterolytic splitting of HChemical science · 2022Article
- Lewis acid protection turns cyanide containing [FeFe]-hydrogenase mimics into proton reduction catalysts.Dalton transactions (Cambridge, England : 2003) · 2022Article
- Ultrafast Photodynamics of Cyano-Functionalized [FeFe] Hydrogenase Model Compounds.The journal of physical chemistry. A · 2018Article
- Cyanide-bridged iron complexes as biomimetics of tri-iron arrangements in maturases of the H cluster of the di-iron hydrogenase.Chemical science · 2016Article
- Diiron azadithiolates as models for the [FeFe]-hydrogenase active site and paradigm for the role of the second coordination sphere.Accounts of chemical research · 2015Article
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Authors and funding
3 authors.
Funding
Abstract
Triarylborane Lewis acids bind [Fe2(pdt)(CO)4(CN)2](2-) [1](2-) (pdt(2-) = 1,3-propanedithiolate) and [Fe2(adt)(CO)4(CN)2](2-) [3](2-) (adt(2-) = 1,3-azadithiolate, HN(CH2S(-))2) to give the 2:1 adducts [Fe2(xdt)(CO)4(CNBAr3)2](2-). Attempts to prepare the 1:1 adducts [1(BAr3)](2-) (Ar = Ph, C6F5) were unsuccessful, but related 1:1 adducts were obtained using the bulky borane B(C6F4-o-C6F5)3 (BAr(F)*3). By virtue of the N-protection by the borane, salts of [Fe2(pdt)(CO)4(CNBAr3)2](2-) sustain protonation to give hydrides that are stable (in contrast to [H1](-)). The hydrides [H1(BAr3)2](-) are 2.5-5 pKa units more acidic than the parent [H1](-). The adducts [1(BAr3)2](2-) oxidize quasi-reversibly around -0.3 V versus Fc(0/+) in contrast to ca. -0.8 V observed for the [1](2-/-) couple. A simplified synthesis of [1](2-), [3](2-), and [Fe2(pdt)(CO)5(CN)](-) ([2](-)) was developed, entailing reaction of the diiron hexacarbonyl complexes with KCN in MeCN.
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