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Borane-protected cyanides as surrogates of H-bonded cyanides in [FeFe]-hydrogenase active site models.
- Source :
-
Inorganic chemistry [Inorg Chem] 2014 Jul 21; Vol. 53 (14), pp. 7241-7. Date of Electronic Publication: 2014 Jul 03. - Publication Year :
- 2014
-
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.
Details
- Language :
- English
- ISSN :
- 1520-510X
- Volume :
- 53
- Issue :
- 14
- Database :
- MEDLINE
- Journal :
- Inorganic chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 24992155
- Full Text :
- https://doi.org/10.1021/ic500470z