{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,16]],"date-time":"2026-10-16T07:25:37Z","timestamp":1792135537483,"version":"4.4.0"},"reference-count":89,"publisher":"American Chemical Society (ACS)","issue":"7","license":[{"start":{"date-parts":[[2020,2,7]],"date-time":"2020-02-07T00:00:00Z","timestamp":1581033600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/pubs.acs.org\/page\/policy\/authorchoice_ccby_termsofuse.html"}],"funder":[{"DOI":"10.13039\/501100000266","name":"Engineering and Physical Sciences Research Council","doi-asserted-by":"publisher","award":["EP\/L015838\/1"],"award-info":[{"award-number":["EP\/L015838\/1"]}],"id":[{"id":"10.13039\/501100000266","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2020,2,19]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Pyridine and related heterocyclic sulfinates have recently emerged as effective nucleophilic coupling partners in palladium-catalyzed cross-coupling reactions with (hetero)aryl halides. These sulfinate reagents are straightforward to prepare, stable to storage and coupling reaction conditions, and deliver efficient reactions, thus offering many advantages, compared to the corresponding boron-derived reagents. Despite the success of these reactions, there are only scant details of the reaction mechanism. In this study, we use structural and kinetic analysis to investigate the mechanism of these important coupling reactions in detail. We compare a pyridine-2-sulfinate with a carbocyclic sulfinate and establish different catalyst resting states, and turnover limiting steps, for the two classes of reagent. For the carbocyclic sulfinate, the aryl bromide oxidative addition complex is the resting state intermediate, and transmetalation is turnover-limiting. In contrast, for the pyridine sulfinate, a chelated Pd(II) sulfinate complex formed post-transmetalation is the resting-state intermediate, and loss of SO2 from this complex is turnover-limiting. We also investigated the role of the basic additive potassium carbonate, the use of which is crucial for efficient reactions, and deduced a dual function in which carbonate is responsible for the removal of free sulfur dioxide from the reaction medium, and the potassium cation plays a role in accelerating transmetalation. In addition, we show that sulfinate homocoupling is responsible for converting Pd(OAc)2 to a catalytically active Pd(0) complex. Together, these studies shed light on the challenges that must be overcome to deliver improved, lower temperature versions of these synthetically important processes.<\/jats:p>","DOI":"10.1021\/jacs.9b13260","type":"journal-article","created":{"date-parts":[[2020,2,7]],"date-time":"2020-02-07T10:10:55Z","timestamp":1581070255000},"page":"3564-3576","source":"Crossref","is-referenced-by-count":43,"title":["Mechanistic\nStudies of the Palladium-Catalyzed Desulfinative\nCross-Coupling of Aryl Bromides and (Hetero)Aryl Sulfinate Salts"],"prefix":"10.1021","volume":"142","author":[{"given":"Antoine","family":"de Gombert","sequence":"first","affiliation":[{"name":"University of Oxford , , Mansfield Road , ,","place":["Oxford, United Kingdom, OX1 4TA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Alasdair I.","family":"McKay","sequence":"additional","affiliation":[{"name":"University of Oxford , , Mansfield Road , ,","place":["Oxford, United Kingdom, OX1 4TA"]},{"name":"University of Melbourne , , , ,","place":["Parkville, VIC, Australia, 3010"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Christopher J.","family":"Davis","sequence":"additional","affiliation":[{"name":"Vertex Pharmaceuticals (Europe), Ltd. , 86-88 Jubilee Avenue , , ,","place":["Abingdon, Oxfordshire, United Kingdom, OX14 4RW"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Katherine M.","family":"Wheelhouse","sequence":"additional","affiliation":[{"name":"Chemical Development, GSK Medicines Research Centre , Gunnels Wood Road , , ,","place":["Stevenage, Hertfordshire, United Kingdom, SG1 2NY"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0636-6471","authenticated-orcid":true,"given":"Michael C.","family":"Willis","sequence":"additional","affiliation":[{"name":"University of Oxford , , Mansfield Road , ,","place":["Oxford, United Kingdom, OX1 4TA"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2020,2,7]]},"reference":[{"key":"2026090313480018800_cit1","doi-asserted-by":"publisher","first-page":"3437","DOI":"10.1016\/S0040-4039(01)95429-2","article-title":"A New Stereospecific\nCross-Coupling\nby the Palladium-Catalyzed Reaction of 1-Alkenylboranes with 1-Alkenyl\nor 1-Alkynyl Halides","volume":"20","author":"Miyaura","year":"1979","journal-title":"Tetrahedron Lett."},{"key":"2026090313480018800_cit2a","doi-asserted-by":"publisher","first-page":"2337","DOI":"10.1039\/b602413k","article-title":"Analysis\nof the Reactions Used for the Preparation of Drug Candidate Molecules","volume":"4","author":"Carey","year":"2006","journal-title":"Org. Biomol. Chem."},{"key":"2026090313480018800_cit2b","doi-asserted-by":"publisher","first-page":"4443","DOI":"10.1021\/acs.jmedchem.5b01409","article-title":"Analysis of Past and Present Synthetic Methodologies\non Medicinal Chemistry: Where Have All the New Reactions Gone?","volume":"59","author":"Brown","year":"2016","journal-title":"J. Med. Chem."},{"key":"2026090313480018800_cit3","doi-asserted-by":"publisher","first-page":"9145","DOI":"10.1021\/jacs.6b03283","article-title":"Protodeboronation\nof Heteroaromatic, Vinyl, and Cyclopropyl Boronic Acids: pH-Rate Profiles,\nAutocatalysis, and Disproportionation","volume":"138","author":"Cox","year":"2016","journal-title":"J. Am.\nChem. Soc."},{"key":"2026090313480018800_cit4","doi-asserted-by":"publisher","first-page":"4437","DOI":"10.1039\/C7SC00675F","article-title":"Pyridine\nSulfinates as General Nucleophilic Coupling Partners in Palladium-Catalyzed\nCross-Coupling Reactions with Aryl Halides","volume":"8","author":"Markovic","year":"2017","journal-title":"Chem. Sci."},{"key":"2026090313480018800_cit5","doi-asserted-by":"publisher","first-page":"6033","DOI":"10.1021\/acs.orglett.7b02944","article-title":"Catalyst\nSelection Facilitates the Use of Heterocyclic Sulfinates as General\nNucleophilic Coupling Partners in Palladium-Catalyzed Coupling Reactions","volume":"19","author":"Markovic","year":"2017","journal-title":"Org. Lett."},{"key":"2026090313480018800_cit6","doi-asserted-by":"publisher","first-page":"15916","DOI":"10.1021\/jacs.8b09595","article-title":"Heterocyclic Allylsulfones as Latent\nHeteroaryl Nucleophiles\nin Palladium-Catalyzed Cross-Coupling Reactions","volume":"140","author":"Markovic","year":"2018","journal-title":"J. Am. Chem. Soc."},{"key":"2026090313480018800_cit7","doi-asserted-by":"publisher","first-page":"408","DOI":"10.1002\/ejoc.201501231","article-title":"Desulfination\nas an Emerging Strategy in Palladium-Catalyzed C-C Coupling Reactions","volume":"2016","author":"Ortgies","year":"2016","journal-title":"Eur. J. Org. Chem."},{"key":"2026090313480018800_cit8","doi-asserted-by":"publisher","first-page":"3273","DOI":"10.1021\/jo00835a021","article-title":"Coupling,\nCarbonylation, and Vinylation Reactions of Aromatic Sulfinic Acids via Organopalladium Intermediates","volume":"35","author":"Garves","year":"1970","journal-title":"J. Org. 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U.S. Patent No. US5159082A, 1992."},{"key":"2026090313480018800_cit13a","doi-asserted-by":"publisher","first-page":"1715","DOI":"10.1055\/s-0033-1339279","article-title":"A Ligand-Free Palladium-Catalyzed\nCross-Coupling of Aryl Sulfinates with Aryl Bromides","volume":"24","author":"Forgione","year":"2013","journal-title":"Synlett"},{"key":"2026090313480018800_cit13b","doi-asserted-by":"publisher","first-page":"10468","DOI":"10.1021\/jo302005s","article-title":"Palladium-Catalyzed Desulfitative Arylation by C-O\nBond Cleavage of Aryl Triflates with Sodium Arylsulfinates","volume":"77","author":"Zhou","year":"2012","journal-title":"J. Org. 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Lett."},{"key":"2026090313480018800_cit13e","doi-asserted-by":"publisher","first-page":"694","DOI":"10.1055\/s-0032-1318151","article-title":"Scope of the Desulfinylative Palladium-Catalyzed\nCross-Coupling of Aryl Sulfinates with Aryl Bromides","volume":"45","author":"Forgione","year":"2013","journal-title":"Synthesis"},{"key":"2026090313480018800_cit14a","doi-asserted-by":"publisher","first-page":"420","DOI":"10.1039\/C2OB27232F","article-title":"An Efficient Tandem Elimination-Cyclization-Desulfitative\nArylation of 2-(Gem-Dibromovinyl)Phenols(Thiophenols) with Sodium\nArylsulfinates","volume":"11","author":"Chen","year":"2013","journal-title":"Org. Biomol. Chem."},{"key":"2026090313480018800_cit14b","doi-asserted-by":"publisher","first-page":"589","DOI":"10.1039\/c3nj41153b","article-title":"Efficient Desulfinylative\nCross-Coupling of Thiophene and Furan Sulfinates with Aryl Bromides\nin Aqueous Media","volume":"37","author":"Se\u0301vigny","year":"2013","journal-title":"New J. 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Soc."},{"key":"2026090313480018800_cit17","doi-asserted-by":"publisher","first-page":"638","DOI":"10.1021\/ja907448t","article-title":"Theoretical Analysis\nof Factors Controlling Pd-Catalyzed Decarboxylative Coupling of Carboxylic\nAcids with Olefins","volume":"132","author":"Zhang","year":"2010","journal-title":"J. Am. Chem. Soc."},{"key":"2026090313480018800_cit18","doi-asserted-by":"publisher","first-page":"12924","DOI":"10.1039\/C9CC06858A","article-title":"SO2 Conversion\nto Sulfones: Development\nand Mechanistic Insights of a Sulfonylative Hiyama Cross-Coupling","volume":"55","author":"Adenot","year":"2019","journal-title":"Chem. Commun."},{"key":"2026090313480018800_cit19a","doi-asserted-by":"publisher","first-page":"1801","DOI":"10.1021\/om2011722","article-title":"Who\nWins: Pesci, Peters, or Deacon?\nIntrinsic Reactivity Orders for Organocuprate Formation via Ligand Decomposition","volume":"31","author":"Sraj","year":"2012","journal-title":"Organometallics"},{"key":"2026090313480018800_cit19b","doi-asserted-by":"publisher","first-page":"12018","DOI":"10.1021\/jo501875n","article-title":"Palladium(II)-Catalyzed\nDesulfitative Synthesis of Aryl Ketones from Sodium Arylsulfinates\nand Nitriles: Scope, Limitations, and Mechanistic Studies","volume":"79","author":"Skillinghaug","year":"2014","journal-title":"J. Org. Chem."},{"key":"2026090313480018800_cit19c","doi-asserted-by":"publisher","first-page":"1455","DOI":"10.1021\/cs200428u","article-title":"Microwave-Assisted\nPalladium(II)-Catalyzed Synthesis of Aryl Ketones from Aryl Sulfinates\nand Direct ESI-MS Studies Thereof","volume":"1","author":"Behrends","year":"2011","journal-title":"ACS Catal."},{"key":"2026090313480018800_cit20a","doi-asserted-by":"publisher","first-page":"8479","DOI":"10.1016\/S0040-4039(02)02073-7","article-title":"A Mild, Convenient\nSynthesis of Sulfinic Acid Salts and Sulfonamides from Alkyl and Aryl\nHalides","volume":"43","author":"Baskin","year":"2002","journal-title":"Tetrahedron Lett."},{"key":"2026090313480018800_cit20b","doi-asserted-by":"publisher","first-page":"10204","DOI":"10.1002\/anie.201404527","article-title":"Palladium-Catalyzed\nSynthesis of Ammonium Sulfinates from Aryl Halides and a Sulfur Dioxide\nSurrogate: a Gas- and Reductant-Free Process","volume":"53","author":"Emmett","year":"2014","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026090313480018800_cit20c","doi-asserted-by":"publisher","first-page":"2652","DOI":"10.1248\/cpb.36.2652","article-title":"A Novel Synthesis of\nAromatic Sulfinic Acids","volume":"36","author":"Kamiyama","year":"1988","journal-title":"Chem. Pharm. Bull."},{"key":"2026090313480018800_cit20d","doi-asserted-by":"publisher","first-page":"533","DOI":"10.1016\/j.tetlet.2015.12.073","article-title":"Synthesis of sodium\naryl sulfinates from aryl bromides employing 1,4-diazabicyclo[2.2.2]octane\nbis(sulfur dioxide) adduct (DABSO) as a bench-stable, gas-free alternative\nto SO2","volume":"57","author":"Skillinghaug","year":"2016","journal-title":"Tetrahedron Lett."},{"key":"2026090313480018800_cit21a","doi-asserted-by":"publisher","first-page":"5822","DOI":"10.1002\/anie.201210252","article-title":"The Impact of Palladium(II)\nReduction Pathways on the Structure and Activity of Palladium(0) Catalysts","volume":"52","author":"Wei","year":"2013","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026090313480018800_cit21b","doi-asserted-by":"publisher","first-page":"3009","DOI":"10.1021\/om00045a012","article-title":"Evidence\nof the Formation of Zerovalent Palladium from Pd(OAc)2 and\nTriphenylphosphine","volume":"11","author":"Amatore","year":"1992","journal-title":"Organometallics"},{"key":"2026090313480018800_cit21c","doi-asserted-by":"publisher","first-page":"6674","DOI":"10.1021\/jo901121e","article-title":"A superior precursor for palladium(0)-based cross-coupling\nand other catalytic reactions","volume":"74","author":"Norton","year":"2009","journal-title":"J. Org. Chem."},{"key":"2026090313480018800_cit21d","doi-asserted-by":"publisher","first-page":"3332","DOI":"10.1021\/ol101106z","article-title":"A Highly Efficient,\nPractical, and General Route for the Synthesis of (R3P)2Pd(0) Structural Evidence on the Reduction Mechanism of Pd(II)\nto Pd(0)","volume":"12","author":"Li","year":"2010","journal-title":"Org. Lett."},{"key":"2026090313480018800_cit22","doi-asserted-by":"publisher","first-page":"314","DOI":"10.1021\/ar980063a","article-title":"Anionic Pd(0) and Pd(II)\nIntermediates in Palladium-Catalyzed\nHeck and Cross-Coupling Reactions","volume":"33","author":"Amatore","year":"2000","journal-title":"Acc. Chem.\nRes."},{"key":"2026090313480018800_cit23","doi-asserted-by":"publisher","first-page":"1338","DOI":"10.1039\/C39860001338","article-title":"\u2018Bis(tripheny1phosphine)palladium:\u2019\nIts Generation, Characterization, and Reactions","author":"Negishi","year":"1986","journal-title":"J. Chem. Soc., Chem. Commun."},{"key":"2026090313480018800_cit24","doi-asserted-by":"publisher","first-page":"4992","DOI":"10.1021\/ja00511a032","article-title":"Palladium-Catalyzed Coupling of Tetraorganotin Compounds\nwith Aryl and Benzyl Halides. Synthetic Utility and Mechanism","volume":"101","author":"Milstein","year":"1979","journal-title":"J. Am. Chem. Soc."},{"key":"2026090313480018800_cit25","doi-asserted-by":"publisher","first-page":"4179","DOI":"10.1021\/ol026988e","article-title":"Ligand-Modulated Palladium Oxidation Catalysis Mechanistic\nInsights into Aerobic Alcohol Oxidation with the Pd(OAc)2 Pyridine Catalyst System","volume":"4","author":"Steinhoff","year":"2002","journal-title":"Org. Lett."},{"key":"2026090313480018800_cit26a","doi-asserted-by":"publisher","first-page":"2359","DOI":"10.1002\/anie.199623591","article-title":"A Route to Pd0 from PdII Metallacycles in Animation and Cross-Coupling\nChemistry","volume":"35","author":"Louie","year":"1996","journal-title":"Angew. Chem., Int. Ed. Engl."},{"key":"2026090313480018800_cit26b","doi-asserted-by":"publisher","first-page":"13978","DOI":"10.1021\/ja037932y","article-title":"Insights into the\nOrigin of High Activity and Stability of Catalysts Derived from Bulky,\nElectron-Rich Monophosphinobiaryl Ligands in the Pd-Catalyzed C-N\nBond Formation","volume":"125","author":"Strieter","year":"2003","journal-title":"J. Am. Chem. Soc."},{"key":"2026090313480018800_cit27","doi-asserted-by":"publisher","first-page":"6653","DOI":"10.1021\/ja035483w","article-title":"Expanding Pd-Catalyzed\nC\u2013N Bond-Forming Processes:\nThe First Amidation of Aryl Sulfonates, Aqueous Amination, and Complementarity\nwith Cu-Catalyzed Reactions","volume":"125","author":"Huang","year":"2003","journal-title":"J. Am. Chem. Soc."},{"key":"2026090313480018800_cit28","doi-asserted-by":"publisher","first-page":"3157","DOI":"10.1021\/om070069g","article-title":"Reactivity\nStudies of Cationic Palladium(II) Phosphine Carboxylate Complexes\nwith Lewis Bases; Substitution versus Cyclometalation","volume":"26","author":"Thirupathi","year":"2007","journal-title":"Organometallics"},{"key":"2026090313480018800_cit29","doi-asserted-by":"publisher","first-page":"805","DOI":"10.1016\/S0277-5387(02)01377-3","article-title":"Insertion of Sulfur Dioxide into\nMetal Carbon Bonds of Chloro(methyl)palladium Complexes","volume":"22","author":"Li","year":"2003","journal-title":"Polyhedron"},{"key":"2026090313480018800_cit30","doi-asserted-by":"publisher","first-page":"m1830","DOI":"10.1107\/S1600536811049889","article-title":"[2,2\u2032-Bis(diphenylphosphanyl)-1,1\u2032-binaphthyl-[kappa]2P,P\u2032]chlorido(4-methylphenylsulfonyl-[kappa]S)palladium(II)\ndichloromethane trisolvate monohydrate","volume":"67","author":"Shrestha","year":"2011","journal-title":"Acta\nCrystallogr., Sect. 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Chem."},{"key":"2026090313480018800_cit32","doi-asserted-by":"publisher","first-page":"6732","DOI":"10.1021\/om900679w","article-title":"A Kinetics Study of the Oxidative\nAddition of Bromobenzene to Pd(PCy3)2 (Cy =\ncyclohexyl) in a Nonpolar Medium: The Influence on Rates of Added\nPCy3 and Bromide Ion","volume":"28","author":"Mitchell","year":"2009","journal-title":"Organometallics"},{"key":"2026090313480018800_cit33","doi-asserted-by":"publisher","first-page":"8141","DOI":"10.1021\/ja900798s","article-title":"Effect\nof Ligand Steric Properties\nand Halide Identity on the Mechanism for Oxidative Addition of Haloarenes\nto Trialkylphosphine Pd(0) Complexes","volume":"131","author":"Barrios-Landeros","year":"2009","journal-title":"J. Am.\nChem. Soc."},{"key":"2026090313480018800_cit34a","doi-asserted-by":"publisher","first-page":"4804","DOI":"10.1021\/ic00099a035","article-title":"Dichlorobis(tricyclohexylphosphine)palladium(II)\nSynthesis and Crystal Structure. An Exceptionally Simple and Efficient\nPreparation of Bis(tricyclohexylphosphine)palladium(0)","volume":"33","author":"Grushin","year":"1994","journal-title":"Inorg. Chem."},{"key":"2026090313480018800_cit34b","doi-asserted-by":"publisher","first-page":"1184","DOI":"10.1021\/ja037928m","article-title":"Synthesis, Structure, Theoretical Studies, and Ligand\nExchange Reactions of Monomeric, T-Shaped Arylpalladium(II) Halide\nComplexes with an Additional, Weak Agostic Interaction","volume":"126","author":"Stambuli","year":"2004","journal-title":"J. Am. Chem. 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Chem."},{"key":"2026090313480018800_cit39","doi-asserted-by":"publisher","first-page":"13571","DOI":"10.1002\/anie.201505918","article-title":"Palladium-Catalyzed\nSynthesis of (Hetero)Aryl Alkyl Sulfones from (Hetero)Aryl Boronic\nAcids, Unactivated Alkyl Halides, and Potassium Metabisulfite","volume":"54","author":"Shavnya","year":"2015","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026090313480018800_cit40","doi-asserted-by":"publisher","first-page":"315","DOI":"10.1002\/anie.197103151","article-title":"Sulfinato Complexes","volume":"10","author":"Vitzthum","year":"1971","journal-title":"Angew. Chem.,\nInt. Ed. Engl."},{"key":"2026090313480018800_cit41","doi-asserted-by":"publisher","first-page":"4116","DOI":"10.1021\/ic010114r","article-title":"Synthesis\nand Insertion Reactions of the Cyclometalated Palladium\u2013Alkyl\nComplexes Pd(CH2CMe2-o-C6H4)L2. 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Chem.\nSoc."},{"key":"2026090313480018800_cit44","doi-asserted-by":"publisher","first-page":"5230","DOI":"10.1021\/om700580d","article-title":"Optimization\nof Procedures for the Syntheses of Bisphosphinepalladium(0)\nPrecursors for Suzuki\u2013Miyaura and Similar Cross-Coupling Catalysis:\nIdentification of 3:1 Coordination Compounds in Catalyst Mixtures\nContaining Pd(0), PCy3, and\/or PMetBu2","volume":"26","author":"Mitchell","year":"2007","journal-title":"Organometallics"},{"key":"2026090313480018800_cit45a","doi-asserted-by":"publisher","first-page":"89","DOI":"10.1016\/0010-8545(93)80025-Z","article-title":"Ligand Steric Properties","volume":"128","author":"Brown","year":"1993","journal-title":"Coord. Chem. 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Chem."},{"key":"2026090313480018800_cit49b","doi-asserted-by":"publisher","first-page":"1233","DOI":"10.1039\/C6SC03924C","article-title":"One-Pot\nPalladium-Catalyzed Synthesis of Sulfonyl Fluorides from Aryl Bromides","volume":"8","author":"Davies","year":"2017","journal-title":"Chem. Sci."},{"key":"2026090313480018800_cit49c","doi-asserted-by":"publisher","first-page":"16372","DOI":"10.1021\/ja1081124","article-title":"Palladium-Catalyzed\nAminosulfonylation of Aryl Halides","volume":"132","author":"Nguyen","year":"2010","journal-title":"J. Am. Chem.\nSoc."},{"key":"2026090313480018800_cit49d","doi-asserted-by":"publisher","first-page":"222","DOI":"10.1039\/C3SC52332B","article-title":"One-Pot Three-Component Sulfone Synthesis Exploiting\nPalladium-Catalysed Aryl Halide Aminosulfonylation","volume":"5","author":"Richards-Taylor","year":"2014","journal-title":"Chem. Sci."},{"key":"2026090313480018800_cit49e","doi-asserted-by":"publisher","first-page":"6226","DOI":"10.1021\/ol403072r","article-title":"Palladium-Catalyzed\nSulfination of Aryl and Heteroaryl Halides: Direct Access to Sulfones\nand Sulfonamides","volume":"15","author":"Shavnya","year":"2013","journal-title":"Org. Lett."},{"key":"2026090313480018800_cit49f","doi-asserted-by":"publisher","first-page":"10037","DOI":"10.1039\/c2cc34957d","article-title":"A Palladium-Catalyzed Reaction of\nAryl Halides, Potassium Metabisulfite, and Hydrazines","volume":"48","author":"Ye","year":"2012","journal-title":"Chem. Commun."},{"key":"2026090313480018800_cit50","doi-asserted-by":"publisher","first-page":"1522","DOI":"10.1002\/aic.690330912","article-title":"Kinetics of the Sodium Carbonate\u2013Sulfur dioxide\nReaction","volume":"33","author":"Kimura","year":"1987","journal-title":"AIChE J."},{"key":"2026090313480018800_cit51a","doi-asserted-by":"publisher","first-page":"215","DOI":"10.1016\/S0360-1285(00)00021-6","article-title":"Sulfation\nPhenomena in Fluidized Bed Combustion Systems","volume":"27","author":"Anthony","year":"2001","journal-title":"Prog. Energy Combust. Sci."},{"key":"2026090313480018800_cit51b","doi-asserted-by":"publisher","first-page":"1454","DOI":"10.1016\/j.ijggc.2011.08.002","article-title":"The Solubility of\nSulfur Dioxide and Carbon Dioxide in an Aqueous Solution of Potassium\nCarbonate","volume":"5","author":"Wappel","year":"2011","journal-title":"Int. J. Greenhouse Gas Control"},{"key":"2026090313480018800_cit52","doi-asserted-by":"publisher","first-page":"3509","DOI":"10.1039\/C4SC01215A","article-title":"An Organic\nCation as a Silver(I) analogue for the Arylation of sp2 and sp3 C\u2013H Bonds with Iodoarenes","volume":"5","author":"Arroniz","year":"2014","journal-title":"Chem. Sci."},{"key":"2026090313480018800_cit53a","doi-asserted-by":"publisher","first-page":"502","DOI":"10.1021\/ed042p502","article-title":"III - Bond energies","volume":"42","author":"Benson","year":"1965","journal-title":"J. Chem.\nEduc."},{"key":"2026090313480018800_cit53b","doi-asserted-by":"publisher","first-page":"465","DOI":"10.1021\/cr60243a001","article-title":"Bond Dissociation Energies by Kinetic\nMethods","volume":"66","author":"Kerr","year":"1966","journal-title":"Chem. 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