First metallamacrocyclic complexes of Pt(IV) with 3,3,3′,3′- tetraalkyl-1,1′-phenylenedicarbonylbis(thioureas): Synthesis by direct or electrolytic oxidative addition of i2, Br2 and Cl 2

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dc.contributor.authorWestra A.N.
dc.contributor.authorBourne S.A.
dc.contributor.authorKoch K.R.
dc.date.accessioned2011-05-15T15:59:07Z
dc.date.available2011-05-15T15:59:07Z
dc.date.issued2005
dc.description.abstractElemental I2 and Br2 cleanly react with the 3 : 3 Pt(II) metallamacrocycle of 3,3,3′,3′-tetra(n-butyl)-1,1′- terephthaloylbis(thiourea) (cis-[PtII3(L p1-S,O)3] 3), in chloroform at room temperature, to yield oxidative addition products; 195Pt NMR studies reveal that a stepwise oxidative addition readily occurs to each of the Pt(II) centres in the metallamacrocycle to yield the mixed valence species cis-[PtII2PtIVI2(Lp1-S,O)3] and cis-[PtIIPtIV2I4(I p1-S,O)3], and the fully oxidised cis-[Pt IV3I6(Lp1-S,O)3] in solution, depending on the mole ratio I2 : 3. Similar results are obtained on treatment of solutions of 3 with elemental Br2. Treatment of the corresponding 2 : 2 Pt(II) complex of 3,3,3′,3′-tetraethyl- 1,1′-isophthaloylbis(thiourea) (cis-[PtII2(L ml-S,O)2] 4) with iodine, results in facile oxidative addition to yield cis-[PtIV2(Lm1-S,O) 2I4] 5, with a trans-Pt(IV)-iodo arrangement. Molecules in the crystal structure of 5 have their trans-Pt(IV)-iodo axes essentially aligned, with very close intermolecular iodide contacts (3.775(1) Å), resulting in chains of weakly bound metallamacrocycles in the solid. An alternative electrolytic synthesis method, using a simple two-compartment glass cell containing 4 and a chosen halide salt in dichloromethane, led to the formation of cis-[PtIV2(Lm1-S,O) 2Br4] 6 and cis-[PtIV2(L m1-S,O)2Cl4] 7, completing characterization of a series of first-reported trans-Pt(IV)-X (X = I, Br, Cl) metallamacrocyclic complexes. © The Royal Society of Chemistry 2005.
dc.description.versionArticle
dc.identifier.citationDalton Transactions
dc.identifier.citation17
dc.identifier.issn14779226
dc.identifier.other10.1039/b507188g
dc.identifier.urihttp://hdl.handle.net/10019.1/11008
dc.subjectBromine
dc.subjectChlorine
dc.subjectElectrolysis
dc.subjectGlass
dc.subjectIodine compounds
dc.subjectNuclear magnetic resonance spectroscopy
dc.subjectOxidation
dc.subjectSolutions
dc.subjectSynthesis (chemical)
dc.subjectUrea
dc.subjectElectrolytic synthesis
dc.subjectMetalloamacrocyclic complexes
dc.subjectOxidative addition
dc.subjectPlatinum compounds
dc.titleFirst metallamacrocyclic complexes of Pt(IV) with 3,3,3′,3′- tetraalkyl-1,1′-phenylenedicarbonylbis(thioureas): Synthesis by direct or electrolytic oxidative addition of i2, Br2 and Cl 2
dc.typeArticle
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