[FeFe]-Hydrogenase Models: Unexpected Variation in Protonation Rate between Dithiolate Bridge Analogues

Jablonskytė, Aušra, Wright, Joseph A. ORCID: https://orcid.org/0000-0001-9603-1001 and Pickett, Christopher J. (2010) [FeFe]-Hydrogenase Models: Unexpected Variation in Protonation Rate between Dithiolate Bridge Analogues. European Journal of Inorganic Chemistry, 2011 (7). pp. 1033-1037. ISSN 1099-0682

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Abstract

The model [FeFe]-hydrogenase subsite Fe2(µ-odt)(CO)4(PMe3)2 (odt = 2-oxapropane-1,3-dithiolate) has been crystallized for the first time, revealing an apical–basal arrangement of the two phosphane groups. Protonation of this species has been studied by a combination of stopped-flow ultraviolet and infrared techniques along with time-resolved NMR spectroscopy. The kinetics of the protonation are similar to those for Fe2(µ-edt)(CO)4(PMe3)2 (edt = ethane-1,2-dithiolate) and are much slower than those for the protonation of Fe2(µ-pdt)(CO)4(PMe3)2 (pdt = propane-1,3-dithiolate). The dithiolate bridge length is therefore not the key determinant of reactivity in these simple model systems.

Item Type:	Article
Faculty \ School:	Faculty of Science > School of Chemistry
Depositing User:	Rhiannon Harvey
Date Deposited:	21 Mar 2012 16:02
Last Modified:	15 Dec 2022 01:29
URI:	https://ueaeprints.uea.ac.uk/id/eprint/38422
DOI:	10.1002/ejic.201001072

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