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dc.creatorTuba, R
dc.creatorTešević, Vele
dc.creatorDinh, LV
dc.creatorHampel, F
dc.creatorGladysz, JA
dc.date.accessioned2018-11-22T00:08:24Z
dc.date.available2018-11-22T00:08:24Z
dc.date.issued2005
dc.identifier.issn1477-9226
dc.identifier.urihttp://cherry.chem.bg.ac.rs/handle/123456789/709
dc.description.abstractReactions of the diphosphine 1,3-C6H4(CH2PH2)(2) and fluorous alkenes H2C=CHRfn (R-fn = (CF2)(n-1)CF3; n = 6, 8) at 75 degrees C in the presence of AIBN give the title ligands 1,3-C6H4(CH2P(CH2CH2Rfn)(2))(2) (3-R-fn) and byproducts 1,3-C6H4(CH3)(CH2P(CH2CH2Rfn)(2)) (4-R-fn) in 1:3 to 1:5 ratios. Workups give 3-R-fn in 4-17% yields. Similar results lre obtained photochemically. Reaction of 1,3-C6H4(CH2Br)(2) and HP(CH2CH2Rf8)(2) (5) at 80 degrees C(neat, 1:2 mol ratio) gives instead of simple substitution the metacyclophane [1,3-C6H4(CH2P(CH2CH2Rf8)(2)CH2-1,3-C6H4CH2P(CH2CH2Rf8)(2)CH2](2+) 2Br(-), which upon treatment with LiAlH4 yields 3-R-f8 (20%), 4-R-f8, and other products. Efforts to better access 3-R-f8, either by altering stoichiometry or using various combinations of the phosphine borane (H3B) PH(CH2CH2Rf8)(2) and base, are unsuccessful. Reactions of 3-R-fn with Pd(O2CCF3)(2) and [IrCl(COE)(2)](2) (COE = cyclooctene) give the palladium and iridium pincer complexes (2,6,1-C6H3(CH2P(CH2CH2Rfn)(2))(2)) Pd(O2CCF3) (10-R-fn; 80-90%) and (2,6,1-C6H3(CH2P(CH2CH2Rf8)(2))(2)) Ir(Cl)(H)(11-R-f8; 29%), which exhibit CF(3)C(6)F(11)3toluene partition coefficients of gt 96 : lt 4. The crystal structure of 10-R-f8 shows CH2CH2Rf8 groups with all-anti conformations that extend in parallel above and below the palladium square plane to create fluorous lattice domains. NMR monitoring shows a precursor to 11-R-f8 that is believed to be a COE adduct.en
dc.publisherRoyal Soc Chemistry, Cambridge
dc.rightsrestrictedAccess
dc.sourceDalton Transactions
dc.titleSynthesis, structure, and reactivity of fluorous phosphorus/carbon/phosphorus pincer ligands and metal complexesen
dc.typearticle
dc.rights.licenseARR
dcterms.abstractТуба, Р; Динх, ЛВ; Хампел, Ф; Тешевић, Веле; Гладyсз, ЈA;
dc.citation.issue13
dc.citation.spage2275
dc.citation.epage2283
dc.identifier.wos000229862400009
dc.identifier.doi10.1039/b502309b
dc.citation.other(13): 2275-2283
dc.citation.rankM21
dc.identifier.pmid15962048
dc.type.versionpublishedVersionen
dc.identifier.scopus2-s2.0-22444438457
dc.identifier.rcubKon_1662


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