caa a22 4500 606180931 CHVBK 20210128100808.0 cr unu---uuuuu 210128e20150101xx s 000 0 eng 10.1007/s10876-014-0790-5 doi (NATIONALLICENCE)springer-10.1007/s10876-014-0790-5 Alkynyl-Phosphine Substituted Fe2S2 Clusters: Synthesis, Structure and Spectroelectrochemical Characterization of a Cluster with a Class III Mixed-Valence [FeFe]3+ Core [Elektronische Daten] [Gregory Newman, Jamil Rahman, Josef Gluyas, Dmitry Yufit, Judith Howard, Paul Low] Phosphinoalkynes P(C≡CC6H4Me-4)Ph2 (1) and P(C≡CC6H4C≡CC6H4Me-4)Ph2 (2) have been prepared from CuI catalysed reactions of the corresponding 1-alkyne and PClPh2. The trimethylamine-N-oxide promoted reaction of PPh3, 1 or 2 with [Fe2(μ-pdt)(CO)6] (pdt=propanedithiolate) affords derivatives [Fe2(μ-pdt)(CO)5{PRPh2}] [R=Ph (3), C≡CC6H4Me (5), C≡CC6H4C≡CC6H4Me (6)] or, at elevated temperatures, [Fe2(μ-pdt)(CO)4(PPh3)2] (4). The cyclic voltammograms of compounds 3 and 4 feature almost fully reversible one-electron oxidation processes and an irreversible reduction, whilst the electrochemical response of the alkynyl phosphine substituted complexes 5 and 6 is irreversible for both oxidation and reduction. IR spectroelectrochemical studies of 4 are consistent with an oxidation processes leading to a delocalized or (Class III) mixed valence [FeFe]3+ core in which the iron centers have an average oxidation state of 1.5. The molecular structures of the alkynyl phosphine substituted clusters 5 and 6 are also reported. Springer Science+Business Media New York, 2014 Iron-only hydrogenase nationallicence Spectroelectrochemistry nationallicence Phosphino alkyne nationallicence Trimethylamine- N -oxide nationallicence Mixed-valence nationallicence Newman Gregory Department of Chemistry, Durham University, South Road, DH1 3LE, Durham, UK aut Rahman Jamil Department of Chemistry, Durham University, South Road, DH1 3LE, Durham, UK aut Gluyas Josef School of Chemistry and Biochemistry, University of Western Australia, Crawley, 6009, Perth, Australia aut Yufit Dmitry Department of Chemistry, Durham University, South Road, DH1 3LE, Durham, UK aut Howard Judith Department of Chemistry, Durham University, South Road, DH1 3LE, Durham, UK aut Low Paul Department of Chemistry, Durham University, South Road, DH1 3LE, Durham, UK aut Journal of Cluster Science Springer US; http://www.springer-ny.com 26/1(2015-01-01), 233-246 1040-7278 26:1<233 2015 26 10876 https://doi.org/10.1007/s10876-014-0790-5 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s10876-014-0790-5 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Newman Gregory Department of Chemistry, Durham University, South Road, DH1 3LE, Durham, UK aut NATIONALLICENCE 700 1- Rahman Jamil Department of Chemistry, Durham University, South Road, DH1 3LE, Durham, UK aut NATIONALLICENCE 700 1- Gluyas Josef School of Chemistry and Biochemistry, University of Western Australia, Crawley, 6009, Perth, Australia aut NATIONALLICENCE 700 1- Yufit Dmitry Department of Chemistry, Durham University, South Road, DH1 3LE, Durham, UK aut NATIONALLICENCE 700 1- Howard Judith Department of Chemistry, Durham University, South Road, DH1 3LE, Durham, UK aut NATIONALLICENCE 700 1- Low Paul Department of Chemistry, Durham University, South Road, DH1 3LE, Durham, UK aut NATIONALLICENCE 773 0- Journal of Cluster Science Springer US; http://www.springer-ny.com 26/1(2015-01-01), 233-246 1040-7278 26:1<233 2015 26 10876