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Preparation, Facile Deprotonation, and Rapid H/D Exchange of the mu-Hydride Diiron Model Complexes of the FeFe -Hydrogenase Containing a Pendant Amine in a Chelating Diphosphine Ligand
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2009 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 48, no 24, 11551-11558 p.Article in journal (Refereed) Published
Abstract [en]

The CO-displacement of [(μ-pdt)Fe2(CO)6] with (Ph2PCH2)2N(n-Pr) in refluxing toluene gave an unsymmetrical chelating complex [(μ-pdt){Fe(CO)3}{Fe(CO)(κ2-Ph2PCH2N(n-Pr)CH2PPh2}] (1) as a major product, together with a small amount of the symmetrical intramolecular bridging complex [(μ-pdt){μ-Ph2PCH2N(n-Pr)CH2PPh2}{Fe(CO)2}2] (2) and the intermolecular bridging complex [{μ,κ11-Ph2PCH2N(n-Pr)CH2PPh2}{(μ-pdt)Fe2(CO)5}2] (3). In contrast, the reaction of [(μ-pdt)Fe2(CO)6] with (Ph2PCH2)2NR (R = n-Pr, Ph) afforded the intermolecular bridging isomers 3 and 4 in the presence of a CO-removing reagent Me3NO·2H2O in CH3CN at room temperature. The molecular structures of 1, 3, and 4, as well as the doubly protonated complex [1(HNHμ)](OTf)2] were determined by X-ray analyses. The protonation processes of 1 with HBF4·Et2O and HOTf were studied in different solvents. The presence of the Hμ···HN interaction in [1(HNHμ)]2+ was studied by relaxation time T1 and spin saturation transfer measurements. The μ-hydride of [1(Hμ)]+ and [1(HNHμ)]2+ undergo facile deprotonation with aniline and rapid H/D exchange with deuterons in solution. In contrast, neither deprotonation nor H/D exchange was detected for [(μ-H)(μ-pdt){Fe(CO)3}{Fe(CO)(κ2-dppp)}]+ ([5(Hμ)]+, dppp = Ph2PCH2CH2CH2PPh2) without internal base.

Place, publisher, year, edition, pages
2009. Vol. 48, no 24, 11551-11558 p.
URN: urn:nbn:se:kth:diva-19027DOI: 10.1021/ic901154mISI: 000272556700016ScopusID: 2-s2.0-73249128865OAI: diva2:337074
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2011-01-25Bibliographically approved

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Sun, Licheng
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