Reactions of halogens with Pt(II) complexes of N-alkyl- and N,N-dialkyl-N′-benzoylthioureas: Oxidative addition and formation of an I2 inclusion compound

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dc.contributor.authorWestra A.N.
dc.contributor.authorBourne S.A.
dc.contributor.authorEsterhuysen C.
dc.contributor.authorKoch K.R.
dc.date.accessioned2011-05-15T15:59:07Z
dc.date.available2011-05-15T15:59:07Z
dc.date.issued2005
dc.description.abstractThe treatment of cis-[PtII(L1a/b-S,O)2] complexes of N,N-diethyl- (HL1a) and N,N-di(n-butyl)-N'- benzoylthiourea (HL1b) with I2 or Br2 in chloroform, leads to rapid oxidative addition to yield several geometric isomers of [PtIV(L-S,O)2X2] (X = I, Br); the reactions can be monitored by 195Pt NMR and UV-visible spectrophotometry. The products cis-[PtIV(L1a-S,O)2I2] 6 and cis-[PtIV(L1a-S,O)2Br2] 7, which have been isolated and structurally characterized, are the first-reported crystal structures of complexes of Pt(IV) with this class of ligand. Molecules of 6 pack such that the I-Pt-1 axes are essentially aligned, with unusually close nearest-neighbour iodide contacts (3.553(1) Å). These short I ⋯ I intermolecular interactions lead to infinite chains of weakly connected molecules in crystals of the compound. No such interactions are evident in the corresponding crystals of 7. Reaction of the Pt(II) complex of N-propyl-N'-benzoylthiourea (H2L2a) cis-/trans-[Pt II(H2L2a-S)2Br2] with Br2 also results in oxidative addition, to yield trans-Pt IV(H2L2a-S)2Br4 9. By contrast, treatment of cis-/trans-[PtII(H2L 2a-S)2I2] with I2 does not lead to an oxidative addition product, yielding instead an interesting iodine inclusion compound of PtII, trans-[PtII(H2L 2a-S)2I2].I2 8. In 8, short intermolecular I ⋯ I distances of 3.453(1) Å between I2 and coordinated iodide ions in trans-[PtII(H2L 2a-S)2I2] molecules, result in infinite chains of weakly linked trans-[PtII(H2L2a-S) 2I2] ⋯ I2 groups in the lattice. However, the empirically estimated bond order of 0.75 for the included I 2 molecules does not support the possible existence of discrete tetraiodide ions (I42-) in the lattice of compound 8. © The Royal Society of Chemistry 2005.
dc.description.versionArticle
dc.identifier.citationDalton Transactions
dc.identifier.citation12
dc.identifier.issn14779226
dc.identifier.other10.1039/b503653d
dc.identifier.urihttp://hdl.handle.net/10019.1/11009
dc.subjectAddition reactions
dc.subjectComplexation
dc.subjectNuclear magnetic resonance spectroscopy
dc.subjectOxidation
dc.subjectReaction kinetics
dc.subjectRedox reactions
dc.subjectUltraviolet spectroscopy
dc.subjectGeometric isomers
dc.subjectInclusion compounds
dc.subjectIntermolecular interactions
dc.subjectLigands
dc.subjectHalogen compounds
dc.titleReactions of halogens with Pt(II) complexes of N-alkyl- and N,N-dialkyl-N′-benzoylthioureas: Oxidative addition and formation of an I2 inclusion compound
dc.typeArticle
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