Phase and Redox Shifted Four Iron/Four Sulfur Clusters: Fluorous Analogs of Metalloenzyme Cofactors
| dc.contributor.utaustinauthor | Mueller, Kory M. | en_US |
| dc.contributor.utaustinauthor | Holliday, Bradley J. | en_US |
| dc.creator | Zhang, Cheng-Pan | en_US |
| dc.creator | Xi, Zhenxing | en_US |
| dc.creator | Mueller, Kory M. | en_US |
| dc.creator | Holliday, Bradley J. | en_US |
| dc.creator | Bazzi, Hassan S. | en_US |
| dc.creator | Gladysz, John A. | en_US |
| dc.date.accessioned | 2016-09-23T18:07:33Z | |
| dc.date.available | 2016-09-23T18:07:33Z | |
| dc.date.issued | 2015-07 | en_US |
| dc.description.abstract | Reactions of (1) [Q](2)[Fe4S4(SC(CH3)(3))(4)] and the fluorous thiols HS(CH2)(n)R-f8 (n = 2, 3; R-f8 = (CF2)(7)CF3)), or (2) [Na](2)[Fe4S4(S(CH2)(n)R-f8)(4)] (n = 2, 3) and [PhCH2P((CH2)(3)R-f6)(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)(2)R-f6/2 (73%) or (2) PhCH2P((CH2)(3)R-f6)(3)/2 (14, 39%), PhCH2P((CH2)(3)R-f6)(3)/3 (15, 63%), and PPN/2 (36%). The educt [Ph3P(CH2)(2)Rf(6)](2)[Fe4S4(SC(CH3)(3))(4)] is in turn prepared from FeCl3, HSC(CH3)(3)/CH3ONa, and [Ph3P( CH2)(2)R-f6][I], and the educts [Na](2)[Fe4S4(S(CH2) nR(f8))(4)] from [Na](2)[Fe4S4(SC(CH3)(3))(4)] and HS(CH2) nRf8. The SCH2 H-1 and C-13 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; e = 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. | en_US |
| dc.description.department | Chemistry | en_US |
| dc.description.sponsorship | Qatar National Research Fund 5-845-1-142 | en_US |
| dc.description.sponsorship | Welch Foundation F-1631 | en_US |
| dc.description.sponsorship | US National Science Foundation CHE-0847763 | en_US |
| dc.identifier | doi:10.15781/T2C824G2W | |
| dc.identifier.citation | Zhang, Cheng-Pan, Zhenxing Xi, Kory M. Mueller, Bradley J. Holliday, Hassan S. Bazzi, and John A. Gladysz. "Phase and redox shifted four iron/four sulfur clusters: fluorous analogs of metalloenzyme cofactors." Dalton Transactions 44, no. 45 (Jul., 2015): 19615-19624. | en_US |
| dc.identifier.doi | 10.1039/c5dt01959a | en_US |
| dc.identifier.issn | 1477-9226 | en_US |
| dc.identifier.uri | http://hdl.handle.net/2152/41169 | |
| dc.language.iso | English | en_US |
| dc.relation.ispartof | en_US | |
| dc.relation.ispartofserial | Dalton Transactions | en_US |
| dc.rights | Administrative deposit of works to Texas ScholarWorks: This works author(s) is or was a University faculty member, student or staff member; this article is already available through open access or the publisher allows a PDF version of the article to be freely posted online. The library makes the deposit as a matter of fair use (for scholarly, educational, and research purposes), and to preserve the work and further secure public access to the works of the University. | en_US |
| dc.rights.restriction | Open | en_US |
| dc.subject | halide-substitution-reactions | en_US |
| dc.subject | disulfide interchange reaction | en_US |
| dc.subject | 4-fe | en_US |
| dc.subject | active-sites | en_US |
| dc.subject | synthetic analogs | en_US |
| dc.subject | tetranuclear clusters | en_US |
| dc.subject | reduced | en_US |
| dc.subject | ferredoxins | en_US |
| dc.subject | ligand substitution | en_US |
| dc.subject | electronic-properties | en_US |
| dc.subject | transfer | en_US |
| dc.subject | catalysts | en_US |
| dc.subject | cubane-type | en_US |
| dc.subject | chemistry, inorganic & nuclear | en_US |
| dc.title | Phase and Redox Shifted Four Iron/Four Sulfur Clusters: Fluorous Analogs of Metalloenzyme Cofactors | en_US |
| dc.type | Article | en_US |