Phase and redox shifted four iron/four sulfur clusters: fluorous analogs of metalloenzyme cofactors

Cheng Pan Zhang, Zhenxing Xi, Kory M. Mueller, Bradley J. Holliday, Hassan S. Bazzi, John A. Gladysz

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Reactions of (1) [Q]2[Fe4S4(SC(CH3)3)4] and the fluorous thiols HS(CH2)nRf8 (n = 2, 3; Rf8 = (CF2)7CF3)), or (2) [Na]2[Fe4S4(S(CH2)nRf8)4] (n = 2, 3) and [PhCH2P((CH2)3Rf6)3][Br] or [PPN][Cl] (PPN = Ph3P⋯N⋯PPh3), give the title compounds [Q]2[Fe4S4(S(CH2)nRf8)4], comprised of a fluorous dianion and in some cases fluorous cations, with (1) Q/n = Ph4P/2 (4, 67%), Ph4P/3 (5, 67%), Me4N/3 (69%), and Ph3P(CH2)2Rf6/2 (73%) or (2) PhCH2P((CH2)3Rf6)3/2 (14, 39%), PhCH2P((CH2)3Rf6)3/3 (15, 63%), and PPN/2 (36%). The educt [Ph3P(CH2)2Rf6]2[Fe4S4(SC(CH3)3)4] is in turn prepared from FeCl3, HSC(CH3)3/CH3ONa, and [Ph3P(CH2)2Rf6][I], and the educts [Na]2[Fe4S4(S(CH2)nRf8)4] from [Na]2[Fe4S4(SC(CH3)3)4] and HS(CH2)nRf8. The SCH2 1H and 13C NMR signals of these paramagnetic salts appear 8.7-10.3 and 32.3-34.9 ppm downfield from those of the corresponding thiols, but the chemical shifts of other signals are nearly normal. The UV-visible spectra show bands similar to those of non-fluorous analogs (290-298 nm and 406-415 nm; ε = 25 700 and 19 200 M-1 cm-1 for 5). The singly fluorous salts are soluble in organic solvents of moderate polarity, but not in fluorous solvents. The doubly fluorous salts 14, 15 are soluble in all fluorous solvents assayed, with partition coefficients of >99.65: <0.35 (CF3C6F11/toluene) and 93.2-93.1: 6.9-6.8 (FC-72/THF). Cyclic voltammograms carried out using a platinum working microelectrode show that 4 is 0.08 V thermodynamically easier to reduce than 5.

Original languageEnglish
Pages (from-to)19615-19624
Number of pages10
JournalDalton Transactions
Issue number45
Publication statusPublished - 30 Jul 2015


ASJC Scopus subject areas

  • Inorganic Chemistry

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