Carbon Sulfur Bond Activation Research Articles

Ring-expansion and desulfurisation of thiophenes with an aluminium(I) reagent.

Reactions of thiophene, 2-methylthiophene, 2-methoxythiophene, 2,3-dimethylthiophene, and benzothiophene with the aluminium(I) complex [{ArNC(Me)2H}Al] (Ar = 2,6-di-isopropylphenyl) are reported. In all cases, carbon-sulfur bond activation and ring-expansion of the heterocycle is observed. For thiophene, we identify a reaction network for desulfurisation that includes an unusual second carbon-sulfur bond activation step.

Transition-metal mediated carbon-sulfur bond activation and transformations: an update.

Carbon-sulfur bond cross-coupling has become more and more attractive as an alternative protocol to establish carbon-carbon and carbon-heteroatom bonds. Diverse transformations through transition-metal-catalyzed C-S bond activation and cleavage have recently been developed. This review summarizes the advances in transition-metal-catalyzed cross-coupling via carbon-sulfur bond activation and cleavage since late 2012 as an update of the critical review on the same topic published in early 2013 (Chem. Soc. Rev., 2013, 42, 599-621), which is presented by the categories of organosulfur compounds, that is, thioesters, thioethers including heteroaryl, aryl, vinyl, alkyl, and alkynyl sulfides, ketene dithioacetals, sulfoxides including DMSO, sulfones, sulfonyl chlorides, sulfinates, thiocyanates, sulfonium salts, sulfonyl hydrazides, sulfonates, thiophene-based compounds, and C[double bond, length as m-dash]S functionality-bearing compounds such as thioureas, thioamides, and carbon disulfide, as well as the mechanistic insights. An overview of C-S bond cleavage reactions with stoichiometric transition-metal reagents is briefly given. Theoretical studies on the reactivity of carbon-sulfur bonds by DFT calculations are also discussed.

Converting Thioether Waste into Organic Semiconductors by Carbon–Sulfur Bond Activation

AbstractA goal for human society is to convert organic waste into valuable materials. Herein, 2‐(methylthio)‐bezothiazole (MTBT), an important organic waste in urban runoff, was catalytically converted into a series of organic semiconductors through carbon–sulfur bond activation. The efficient conversion of various substrates with different aromatic moieties and reacting functional groups (tin and boron) proved the generality of this novel diarylation Liebeskind–Srogl methodology. Moreover, the resulting organic semiconductors showed excellent performance in field effect transistors and cell imaging. This contribution presents an excellent example of converting organic waste into valuable materials and may open a new avenue to utilizing widely available aromatic thioethers.

Converting Thioether Waste into Organic Semiconductors by Carbon-Sulfur Bond Activation.

A goal for human society is to convert organic waste into valuable materials. Herein, 2-(methylthio)-bezothiazole (MTBT), an important organic waste in urban runoff, was catalytically converted into a series of organic semiconductors through carbon-sulfur bond activation. The efficient conversion of various substrates with different aromatic moieties and reacting functional groups (tin and boron) proved the generality of this novel diarylation Liebeskind-Srogl methodology. Moreover, the resulting organic semiconductors showed excellent performance in field effect transistors and cell imaging. This contribution presents an excellent example of converting organic waste into valuable materials and may open a new avenue to utilizing widely available aromatic thioethers.

Palladium-catalyzed, unsymmetrical homocoupling of thiophenes via carbon-sulfur bond activation: a new avenue to homocoupling reactions.

The Pd-catalyzed, CN-directed unsymmetrical synthesis of 2,4'-bithiophenes via an unprecedented homocoupling reaction is described. The NH2/CN/SMe arrangement breaks the routine. The cooperative performance of the functional groups in thiophenes would open up a new vision in the field of metal catalysis homocoupling reactions by joining the electrophilic and nucleophilic motifs of the substrate. Furthermore, it is found that the α-chelating effect of the carbonyl group in amino thiophene offers a new class of synthetic protocols for C-N cross-coupling with arylboronic acids. The bidentate N,O-chelation provides a series of advantages such as copper-catalyzed, ligand- and base-free under open-flask conditions. Interestingly, the combination of the C-N cross-coupling/homocoupling reactions in a domino fashion led to the bithiophene adducts featuring the C(Ar)-N bond cleavage in the nitrogen that bridged between the two thiophene units.

Correction to Room-Temperature Carbon–Sulfur Bond Activation by a Reactive (dippe)Pd Fragment

ADVERTISEMENT RETURN TO ISSUEPREVAddition/CorrectionORIGINAL ARTICLEThis notice is a correctionCorrection to Room-Temperature Carbon–Sulfur Bond Activation by a Reactive (dippe)Pd FragmentLloyd Munjanja, William W. Brennessel, and William D. Jones*Cite this: Organometallics 2015, 34, 19, 4781Publication Date (Web):September 10, 2015Publication History Published online10 September 2015Published inissue 12 October 2015https://doi.org/10.1021/acs.organomet.5b00752Copyright © 2015 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views553Altmetric-Citations1LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (99 KB) Get e-AlertsSUBJECTS:Bond activation Get e-Alerts

Room-Temperature Carbon–Sulfur Bond Activation by a Reactive (dippe)Pd Fragment

The reactivity of [Pd(dippe)(μ-H)]2 (1) and [(μ-dippe)Pd]2 (2) (dippe = 1,2-bis(diisopropylphosphino)ethane) toward C–S bonds in thiophene derivatives and thioethers was investigated, which led to C–S bond activation products. The thiapalladacycles derived from thiophenic substrates were fully characterized by 1H, 31P, and 13C NMR spectroscopy, elemental analysis, and X-ray diffraction. The stability of the C–S insertion products was probed by performing competition experiments which follow the thermodynamic stability order (dippe)Pd(κ2C,S-benzothiophene) (6) > (dippe)Pd(κ2C,S-dibenzothiophene) (8) > (dippe)Pd(κ2C,S-thiophene) (3). The reactivity of the thiapalladacycles with small molecules such as H2, CO, and alkynes was investigated.

Gas-phase reactivity of aluminum cluster anions with ethanethiol: Carbon–sulfur bond activation

We report a joint experimental and theoretical study of the gas-phase reactivity of Al cluster anions with ethanethiol (EtSH) in a fast-flow tube reactor. Nearly all Aln- clusters observed are reactive at the presence of sufficient EtSH molecules with minor exceptions. Sulfide species AlnSm- dominate the observed reaction products, indicating C–S bond activation of EtSH. By using DFT calculations we provide an in-depth analysis on the interesting cluster reactivity of Aln- with EtSH. It is demonstrated that the desulfurization leading to AlnSm- products is associated with the dehydrogen processes successively initiated by S–H bond cleavage and C–H bond cracking.

Transition-metal mediated carbon–sulfur bond activation and transformations

C-S bond activation, cleavage and transformations by means of transition metal compounds have recently become more and more important in the petroleum industry and synthetic chemistry. Homogeneous transition metal compounds have been investigated in order to provide the fundamental insight into the C-S bond cleavage in problematic organosulfur compounds such as thiophene, benzo- and dibenzothiophene derivatives. Rendering transition-metal mediated reactions with organosulfur compounds catalytic may provide promising routes to deep hydrodesulfurization of petroleum feedstocks, and offer potentially useful synthetic protocols for cross-couplings and biomimetic organic synthesis. During the last few decades increasing work was documented on C-S bond activation and transformations by means of transition metal compounds. This review summarizes the recent advances in C-S bond cleavage via the insertion of transition metals into the inert C-S bonds of these problematic organosulfur compounds, and transition-metal mediated C-S bond transformations via C-S activation through cross-couplings of thioesters, ketene dithioacetals, sulfonyl chlorides, and other diverse organosulfur compounds.

Carbon–sulfur bond activation of thiophenes by [W(NPh){o-(Me3SiN)2C6H4}(pyridine)2

Addition of thiophene, 2-methylthiophene, benzothiophene or 3-methylthiophene to [W(NPh){o-(Me3SiN)2C6H 4}(C5H5N)2] 1 affords the metallathiacycle complexes [{o-(Me3SiN)2C6H4 }(NPh)W(SC4H4)] 2, [{o-(Me3SiN)2C6H4 }(NPh)W(SC5H6)] 3, [{o-(Me3SiN)2C6H4 }(NPh)W(SC8H6)] 4 and [{o-(Me3SiN)2C6H4 }(NPh)W(SC5H6)] 5a and 5b, providing the first example of thiophene C–S bond activation by a W(IV) metal complex.

Carbon–oxygen and carbon–sulfur bond activation of vinyl esters, ethers and sulfides by low valent ruthenium complexes †

[Ru(cod)(cot)] (1) (cod: 1,5-cyclooctadiene, cot: 1,3,5-cyclooctatriene) reacts with phenyl vinyl ether and vinyl sulfides in the presence of the bidentate depe ligand affording the zerovalent (η2-vinyl ether or sulfide)ruthenium(0) complexes, [Ru(η2-C2H3YR)(cod)(depe)] [RY = PhO (2a), PhS (2b), PhCH2S (2c), EtS (2d), Me2CHS (2e), depe: 1,2-bis(diethylphosphino)ethane]. Whereas the vinyl ether or sulfide ligand is selectively displaced in 2a, 2d and 2e by monodentate phosphines giving [Ru(cod)(depe)L] [L = PMe3 (3a), PMe2Ph (3b)], partial exchange reactions of either the vinyl sulfide ligand or cod take place for 2b and 2c affording 3a and b and [Ru(η2-C2H3SR)(depe)(L)2] [L = PMe3, R = Ph (4a), L = PMe2Ph, R = Ph (4b); L = PMe3, R = CH2Ph (4c)]. The intermolecular C–S bond cleavage takes place in 4a promoted by MeI to form [Ru(I)(η1-C2H3)(depe)(PMe3)2] 5 with liberation of MeSPh. On the other hand, reactions of 1 with vinyl carboxylates in the presence of tertiary phosphines such as PMe3, PEt3 or depe give a series of (η1-vinyl)ruthenium(II) complexes cis-[Ru(η1-C2H3)(η1-OCOR′)(PMe3)4] [R′ = Me (6a), Et (6b), tBu (6c), Ph (6d)], mer-[Ru(η1-C2H3)(η2-OCOR′)(PEt3)3] [R′ = Me (7a), Et (7b), tBu (7c), Ph (7d), C(Me)CH2 (7e)], trans-[Ru(η1-C2H3)(η1-OCOR′)(depe)2] [R′ = Me (8a), Et (8b), tBu (8c), Ph (8d), C(Me)CH2 (8e)]. The structures of 2a, 2b, 3a, and 8a have been determined by X-ray crystallography. A mechanism including prior co-ordination of the vinylic moiety has been proposed for the C–O bond cleavage reaction on ruthenium(0).

Theory of Carbon-Sulfur Bond Activation by Small Metal Sulfide Particles

Elementary reaction steps for the catalytic cycle of thiophene desulfurization on Ni3Sy and Ni4Sy clusters are investigated using d. functional quantum chem. calcns. The Ni3S2 cluster is active while the Ni4Sy cluster is relatively inactive for HDS catalysis. Adsorption and overall reaction energies are computed on complete geometry-optimized cluster-adsorbate systems. The nickel-sulfide cluster is found to significantly reorganize upon interaction with adsorbates. Sulfur readily rearranges between 3-fold and 2-fold binding sites. Hydrogen adsorbs mol. and dissocs. heterolytically over Ni3S2 to form both adsorbed sulfhydryl (SH) and hydryl (MH) species. The presence of coadsorbed hydrogen affects both the heat of adsorption and the coordination of thiophene. On the bare Ni3S2 cluster thiophene binds with h4-coordination, while in the presence of coadsorbed hydrogen thiophene prefers the h1 site. 2,5-Dihydrothiophene (DHT) adsorbs somewhat more strongly than thiophene on the Ni3S2 cluster. In the preferred h3 configuration, the ethylene moiety of DHT adsorbs at one nickel atom site while its sulfur adsorbs at the neighboring nickel atom site. For the HDS cycles initiated by h1 or h4 thiophene adsorption,the energy change assocd. with the carbon-sulfur bond scission step of adsorbed dihydrothiophene and that for the removal of sulfur via H2S are the most endothermic steps and are speculated to be rate-limiting. Their comparable values indicate that the two steps compete. The cycle which is initiated by the removal of sulfur from Ni3S2 is energetically unfavorable. [on SciFinder (R)]