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Synthesis and characterization of carboxy-functionalized diiron model complexes of FeFe -hydrogenases: Decarboxylation of Ph2PCH2COOH promoted by a diiron azadithiolate complex
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2009 (English)In: Journal of Organometallic Chemistry, ISSN 0022-328X, E-ISSN 1872-8561, Vol. 694, no 15, 2309-2314 p.Article in journal (Refereed) Published
Abstract [en]

Two carboxy-functionalized diiron complexes [{(mu-SCH2)(2)X}{Fe(CO)(3)}{Fe(CO)(2)L}] (X = NC3H7, L = Ph2PCH2CH2COOH, 4; X = CH2, L = Ph2PCH2COOH, 5) were prepared, as biomimetic models of the [FeFe] hydrogenase active site, from the CO-replacement of [{(mu-SCH2)(2)NC3H7}Fe-2(CO)(6)] (1) and (mu-pdt)Fe-2(CO)(6) (2) by phosphine ligands in CH3CN at 40 degrees C, respectively. In contrast, the reaction of 1 with Ph2PCH2COOH under the same condition afforded complex [{(mu-SCH2)(2)NC3H7}{Fe(CO)(3)}{Fe- (CO)(2)(Ph2PCH3)}] (3) with a decarboxylated phosphine ligand. The molecular structures of complexes 3-5 were determined by X-ray crystallographic analyses, which show that they have similar frameworks with the phosphine ligand on the apical position. The interesting C-H center dot center dot center dot S contacts between the methylene hydrogen atoms of the PhCH2COOH ligand and the mu-S atoms of the pdt-bridge are found in the crystal of 5. According to the experimental evidence, a plausible mechanism, via sequential phosphine coordination, N-protonation, and decarboxylation steps, is proposed for the formation of 3 and for explanation of the contrastive reactivities of the adt- (2-aza-1,3-propanedithiolato) and the pdt-(1,3-propanedithiolato) bridged diiron complexes toward decarboxylation of the Ph2PCH2COOH ligand.

Place, publisher, year, edition, pages
2009. Vol. 694, no 15, 2309-2314 p.
URN: urn:nbn:se:kth:diva-18484DOI: 10.1016/j.jorganchem.2009.03.039ISI: 000266638700003ScopusID: 2-s2.0-66149156253OAI: diva2:336531
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2011-01-28Bibliographically approved

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Sun, Licheng
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