Structural and Spectroscopic Features of Mixed Valent Fe(II)Fe(I) Complexes and Factors Related to the Rotated Configuration of Diiron Hydrogenase.
Summary of "Structural and Spectroscopic Features of Mixed Valent Fe(II)Fe(I) Complexes and Factors Related to the Rotated Configuration of Diiron Hydrogenase."
The compounds of this study have yielded to complementary structural, spectroscopic (Mössbauer, EPR/ENDOR, IR), and computational probes that illustrate the fine control of electronic and steric features that are involved in the two structural forms of (µ-SRS)[Fe(CO)(2)PMe(3)](2)(0,+) complexes. The installation of bridgehead bulk in the -SCH(2)CR(2)CH(2)S- dithiolate (R = Me, Et) model complexes produces 6-membered FeS(2)C(3) cyclohexane-type rings that produce substantial distortions in Fe(I)Fe(I) precursors. Both the innocent (Fc(+)) and the non-innocent or incipient (NO(+)/CO exchange) oxidations result in complexes with inequivalent iron centers in contrast to the Fe(I)Fe(I) derivatives. In the Fe(II)Fe(I) complexes of S = ½, there is complete inversion of one square pyramid relative to the other with strong super hyperfine coupling to one PMe(3) and weak SHFC to the other. Remarkably, diamagnetic complexes deriving from isoelectronic replacement of CO by NO(+), {(µ-SRS)[Fe(CO)(2)PMe(3)] [Fe(CO)(NO)PMe(3)](+)}, are also rotated, and exist in only one isomeric form with the -SCH(2)CR(2)CH(2)S- dithiolates, in contrast to R = H (J.Am. Chem. Soc. 2008, 130, 12021-12030). The results and redox levels determined from the extensive spectroscopic analyses have been corroborated by gas-phase DFT calculations, with the primary spin density either localized on the rotated iron in the case of the S = ½ compound, or delocalized over the {Fe(NO)} unit in the S = 0 complex. In the latter case the nitrosyl has effectively shifted electron density from the Fe(I)Fe(I) bond, repositioning it onto the spin coupled Fe-N-O unit such that steric repulsion is sufficient to induce the rotated structure in the Fe(II)-{Fe(I)(•NO)}(8) derivatives.
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Journal Details
This article was published in the following journal.
Name: Journal of the American Chemical Society
ISSN: 1520-5126
Pages:
Links
- PubMed Source: http://www.ncbi.nlm.nih.gov/pubmed/22774845
- DOI: http://dx.doi.org/10.1021/ja304866r
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