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dc.contributor.authorDowling-Mitchell, Sacha A.M.
dc.contributor.authorHenderson, William
dc.contributor.authorTiekink, Edward R. T.
dc.contributor.authorPetrakopoulou, J.
dc.contributor.authorSigalas, Michael P.
dc.date.accessioned2013-04-24T03:13:03Z
dc.date.available2013-04-24T03:13:03Z
dc.date.issued2012
dc.identifier.citationDowling-Mitchell, S.A.M., Henderson, W., Tiekink, E.R.T., Petrakopoulou, J. & Sigalas,M.P. (2012). Organometallics, 31(13), 4662-4669.en_NZ
dc.identifier.issn0276-7333
dc.identifier.urihttps://hdl.handle.net/10289/7519
dc.description.abstractReactions of the platinum complexes cis-[PtCl₂(PPh₃)₂ ], [PtCl₂(dppf)], or [PtCl₂(dppe)], and the palladium complexes, [PdCl₂(PPh₃)₂] or [PdCl₂(dppe)], with bis(cyanomethyl)sulfone NCCH₂SO₂ CH₂CN in methanol with added trimethylamine base gave the new cyano-substituted metallathietane-3,3- dioxide complexes [M{CH(CN)SO₂ CH(CN)}L₂ ] (M = Pd, Pt) in good yields and purities. ¹H and ³¹P{¹H} NMR spectroscopy indicates that (in the majority of cases) the products are formed as a mixture of cis and trans isomers, with regard to the disposition of the cyano groups across the four-membered ring. An X-ray structure determination on a crystal of [Pd{CH(CN)SO₂CH(CN)}(PPh₃)₂] showed it to be of the cis isomer, the first structurally characterized cis isomer of this type of complex. The four-membered palladacyclic ring is highly planar, in contrast to other metallathietane-3,3-dioxide complexes that have puckered rings. Factors influencing the relative abundances of the two isomers of [Pd{CH(CN)SO₂CH(CN)}(PR₃)₂] have been investigated by means of NMR spectroscopy and DFT calculations.en_NZ
dc.language.isoen
dc.publisherAmerican Chemical Society (ACS)en_NZ
dc.titleCis-trans ring substituent isomerism in cyano-substituted metallathietane-3,3-dioxide complexes of platinum(II) and palladium(II)en_NZ
dc.typeJournal Articleen_NZ
dc.identifier.doi10.1021/om2011497en_NZ
dc.relation.isPartOfOrganometallicsen_NZ
pubs.begin-page4662en_NZ
pubs.elements-id37807
pubs.end-page4669en_NZ
pubs.issue13en_NZ
pubs.volume31en_NZ


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