59507-56-1Relevant articles and documents
Polycarbon Disulfides SCnS (n = 1-3) and Their Protonated and Methylated Forms (HCnS2+ and CH3CnS2+): Tandem Mass Spectrometry and ab Initio MO Study
Wong, Ming Wah,Wentrup, Curt,Flammang, Robert
, p. 16849 - 16856 (1995)
Dissociative ionization of 4,5-bis(methylthio)-1,2-dithiole-3-thione (1) has allowed the detection of a series of carbon disulfide radical cations, SCnS.+ (n = 1-3), and their S-methylated forms, CH3SCnS+, in the gas phase of a mass spectrometer.The connectivities and stabilities of these ions and the corresponding neutrals have been probed by collisional activation (CA) and neutralization-reionization (NR) mass spectrometry.Moreover, the sites of protonation and cationic methylation of the polycarbon disulfides have been investigated by a combination of flash vacuum pyrolysis, chemical ionization, and CAMS (FVP/CI/MS/MS).The experimental results are supported by ab initio MO calculations at the QCISD(T)/6-311+G(2d,p) + ZPVE level.Both experiments and calculations indicate that the most favorable site of protonation and methylation is the carbon atom for C2S2 and C3S2 but a sulfur atom for CS2.The proton affinities (298 K) of C2S2 and C3S2 are predicted to be 842 and 818 kJ mol-1, respectively.
A simple and safe procedure for bis(methylthio)- and bis(ethylthio)acetylene
Verkruijsse,Brandsma
, p. 818 - 818 (1991)
The acetylenic derivatives bis(methylthio)- and bis(ethylthio)acetylene were obtained in high yield by addition of alkyl thiocyanates to solutions of sodium acetylide in liquid ammonia.
A novel palladium-catalyzed cross-coupling of thiomethylated alkynes with functionalized organozinc reagents
Melzig, Laurin,Stemper, Jeremy,Knochel, Paul
experimental part, p. 2085 - 2091 (2010/08/19)
A range of methylthio-substituted acetylenes undergo smooth palladium-catalyzed cross-coupling reactions with functionalized aryl-, heteroaryl-, and alkylzinc reagents using the Pd(OAc)2/DPE-Phos catalytic system at 25 or 50 C without the need for copper salts. Georg Thieme Verlag Stuttgart.
Vinylidene, acetylide, and carbene complexes from reactions of 2,5-dithiahex-3-yne (MeSC≡CSMe) with Cp(PMe3)2Ru+
Miller, David C.,Angelici, Robert J.
, p. 79 - 89 (2008/10/08)
The alkyne MeSC≡CSMe initially displaces Cl- in Cp(PMe3)2RuCl at room temperature in MeOH to form the sulfur-bound alkyne complex {Cp(PMe3)2Ru[S(Me)C≡CSMe]}PF6 (1). When it is warmed, 1 rearranges to the vinylidene complex [Cp(PMe3)2Ru=C=C(SMe)2]PF6 (2). Complex 2 is reduced by Na[HBEt3] or Na/Hg to give the thioacetylide Cp(PMe3)2Ru-C≡CSMe (5) and MeSSMe. The vinylidene complexes [Cp(PMe3)2Ru=C=C(R)(SMe)]+ (6, R = H; 7, R = Me) are formed by electrophilic addition to the β-carbon of the thioacetylide 5. Addition of CuCl to 5 forms Cp(PMe3)2Ru(C≡CSMe)(CuCl) (8), in which the copper is π-bound through the C≡C group. Reaction of 6 with methanol and ethanol yields the alkoxycarbene complexes [Cp(PMe3)2Ru=C(OR)(CH2SMe)]BF4 (11a, R = Me; 11b, R = Et). Deprotonation of 11a with NaOMe yields the vinyl complex Cp(PMe3)2Ru[C(OMe)=C(H)SMe] (12). Addition of [Me3O]BF4 to complexes 6 and 7 yields the first examples of sulfoniovinylidene dicationic complexes [Cp(PMe3)2Ru=C=C(R)(SMe2)](BF4) 2 (9, R = H; 10, R = Me). An X-ray diffraction investigation shows that 9 crystallizes in space group P21/n with a = 16.641 (2) A?, b = 8.861 (1) A?, c = 18.168 (2) A?, β = 114.80 (1)°, and Z = 4. Complexes 7 and 10 undergo one- and two-electron reductions, respectively, to give the acetylide Cp(PMe3)2Ru-C≡CMe (14) and MeSSMe (for 7) or SMe2 (for 10). Complexes 6 and 9 are readily deprotonated to give 5 and the sulfonioacetylide [Cp(PMe3)2Ru-C≡CSMe2]BF4 (13), respectively. Mechanisms of the reactions and structural features of the vinylidenes are discussed.
