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      Cis-trans ring substituent isomerism in cyano-substituted metallathietane-3,3-dioxide complexes of platinum(II) and palladium(II)

      Dowling-Mitchell, Sacha A.M.; Henderson, William; Tiekink, Edward R. T.; Petrakopoulou, J.; Sigalas, Michael P.
      DOI
       10.1021/om2011497
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      Dowling-Mitchell, S.A.M., Henderson, W., Tiekink, E.R.T., Petrakopoulou, J. & Sigalas,M.P. (2012). Organometallics, 31(13), 4662-4669.
      Permanent Research Commons link: https://hdl.handle.net/10289/7519
      Abstract
      Reactions 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.
      Date
      2012
      Type
      Journal Article
      Publisher
      American Chemical Society (ACS)
      Collections
      • Science and Engineering Papers [3019]
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