110693-92-0Relevant academic research and scientific papers
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,Sigalas, Michael P.
, p. 4662 - 4669 (2012/09/08)
Reactions of the platinum complexes cis-[PtCl2(PPh 3)2], [PtCl2(dppf)], or [PtCl 2(dppe)], and the palladium complexes, [PdCl2(PPh 3)2] or [PdCl2(dppe)], with bis(cyanomethyl)sulfone NCCH2SO2CH2CN in methanol with added trimethylamine base gave the new cyano-substituted metallathietane-3,3-dioxide complexes [M{CH(CN)SO2CH(CN)}L 2] (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)}(PR 3)2] have been investigated by means of NMR spectroscopy and DFT calculations.
