498533-91-8Relevant academic research and scientific papers
Nucleophilic addition of bifunctional sulfimidosulfides to platinum(IV)-coordinated nitriles
Makarycheva-Mikhailova,Selivanov,Bokach,Kukushkin,Kelly,Pombeiro
, p. 1681 - 1685 (2007/10/03)
Reactions of the platinum(IV) nitrile complexes [PtCl4(RCN) 2] (R = Me, CH2Ph, Ph) with 1,2- and 1,4-PhS(=NH)C 6H4SPh in CH2Cl2 afforded addition products of sulfimides and coordinated nitriles, viz., the [PtCl 4{NH=C(R)N=S(Ph)(C6H4SPh)}2] complexes. The latter were isolated in 75-90% yielks and characterized by elemental analysis, positive-ion FAB mass spectrometry, IR spectroscopy, and 1H and 13C1H NMR spectroscopy. The temperature dependence of the 1H NMR spectra of the model [PtCl 4{NH=C(R)N=SPh2}2] complexes (R = Me, Et) in CD2Cl2 studied in a temperature range from +40 to -70°C demonstrated that E-Z isomerization of the ligands is a dynamic process in a range from +40 to -10°C. The activation free energy of this process was calculated.
Platinum(IV)-mediated nitrile-sulfimide coupling: A route to heterodiazadienes
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.
, p. 301 - 311 (2008/10/08)
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 HCI 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.
