Platinum(IV)-Mediated Nitrile−Sulfimide Coupling:  A Route to Heterodiazadienes

Pt(IV)-mediated addition of the sulfimide Ph2SNH and the mixed sulfide/sulfimides o- and p-{PhS(NH)}(PhS)C6H4 by the SNH group to the metal-bound nitriles in the platinum(IV) complexes [PtCl4(RCN)2] proceeds smoothly at room temperature in CH2Cl2 and results in the formation of the heterodiazadie...

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Veröffentlicht in:Inorganic chemistry 2003-01, Vol.42 (2), p.301-311
Hauptverfasser: Makarycheva-Mikhailova, Anastassiya V, Bokach, Nadezhda A, Kukushkin, Vadim Yu, Kelly, Paul F, Gilby, Liam M, Kuznetsov, Maxim L, Holmes, Kathryn E, Haukka, Matti, Parr, Jonathan, Stonehouse, Julia M, Elsegood, Mark R. J, Pombeiro, Armando J. L
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Sprache:eng
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Zusammenfassung:Pt(IV)-mediated addition of the sulfimide Ph2SNH and the mixed sulfide/sulfimides o- and p-{PhS(NH)}(PhS)C6H4 by the SNH group to the metal-bound nitriles in the platinum(IV) complexes [PtCl4(RCN)2] proceeds smoothly at room temperature in CH2Cl2 and results in the formation of the heterodiazadiene compounds [PtCl4{NHC(R)NSR‘Ph}2] (R‘ = Ph, R = Me, Et, CH2Ph, Ph; R‘ = o- and p-(PhS)C6H4; R = Et). While trans-[PtCl4(RCN)2] (R = Et, CH2Ph, Ph) reacting with Ph2SNH leads exclusively to trans-[PtCl4{NHC(R)NSPh2}2], cis/trans-[PtCl4(MeCN)2] leads to cis/trans mixtures of [PtCl4{NHC(Me)NSPh2}2] and the latter have been separated by column chromatography. Theoretical calculations at both HF//HF and MP2//HF levels for the cis and trans isomers of [PtCl4{NHC(Me)NSMe2}2] indicate a higher stability for the latter. Compounds trans-[PtCl4{E-NHC(R)NSPh2}2] (R = Me, Et) and cis-[PtCl4{E-NHC(Me)NSPh2}{Z-NHC(Me)NSPh2}] have been characterized by X-ray crystallography. The complexes [PtCl4{NHC(R)NSPh2}2] undergo hydrolysis when treated with HCl in nondried CH2Cl2 to achieve the amidines [PtCl4{NHC(NH2)R}2] (the compound with R = Et has been structurally characterized) and Ph2SO. The heterodiazadiene ligands, formed upon Pt(IV)-mediated RCN/sulfimide coupling, can be liberated from their platinum(IV) complexes [PtCl4{NHC(R)NSR‘Ph}2] by reaction with Ph2PCH2CH2PPh2 (dppe) giving free NHC(R)SR‘Ph and the dppe oxides, which constitutes a novel route for such rare types of heterodiazadienes whose number has also been extended. The hybrid sulfide/sulfimide species o- and p-{PhS(NH)}(PhS)C6H4 also react with the Pt(II) nitrile complex [PtCl2(MeCN)2] but the couplingin contrast to the Pt(IV) speciesgives the chelates [PtCl2{NHC(Me)NS(Ph)C6H4SPh}]. The X-ray crystal structure of [PtCl2{NHC(Me)NS(Ph)C6H4SPh-o}] reveals the bond parameters within the metallacycle and shows an unusual close interaction of the sulfide sulfur atom with the platinum.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic025960w