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Why does the synthesis of N-phenylbenzamide from benzenesulfinate and phenylisocyanate via the palladium-mediated Extrusion–Insertion pathway not work? A mechanistic exploration
The gas-phase extrusion–insertion (ExIn) reactions of the palladium complexes [(phen)nPd(O2SC6H5)]+ (phen = 1,10-phenanthroline, n = 1 or 2), were investigated in the gas phase by multistage mass spectrometry (MSn) experiments consisting of electrospray ionisation and a linear ion trap combined with...
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Published in: | Critical studies in media communication 2023-01, Vol.76 (1), p.49 |
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creator | Yang, Yang Canty, Allan J Richard A. J. O’Hair |
description | The gas-phase extrusion–insertion (ExIn) reactions of the palladium complexes [(phen)nPd(O2SC6H5)]+ (phen = 1,10-phenanthroline, n = 1 or 2), were investigated in the gas phase by multistage mass spectrometry (MSn) experiments consisting of electrospray ionisation and a linear ion trap combined with density functional theory (DFT) calculations. Desulfination of palladium sulfinate cations under collision-induced dissociation (CID) generates the organopalladium intermediates [(phen)nPd(C6H5)]+. Of these two organometallic cations, only [(phen)Pd(C6H5)]+ reacts with phenyl isocyanate via insertion to yield [(phen)Pd(NPhC(O)C6H5)]+. The formation of a coordinated amidate anion is supported by DFT calculations. In exploring this reactivity in the solution phase, we found that heating a mixture of benzenesulfinic acid, phenylisocyanate and palladium trifluoroacetate under a range of different conditions (ligand free versus with ligand, different solvents, addition of acid or base) failed to lead to the formation N-phenyl-benzamide in all cases. Instead, biphenyl was formed and could be isolated in a yield of 46%. DFT calculations using a solvent continuum reveal that the barrier associated with the insertion reaction lies above the competing sequential reactions of desulfination of a second phenyl sulfinate followed by reductive elimination of biphenyl. |
doi_str_mv | 10.1071/CH22209 |
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A mechanistic exploration</title><source>Taylor and Francis Social Sciences and Humanities Collection</source><creator>Yang, Yang ; Canty, Allan J ; Richard A. J. O’Hair</creator><creatorcontrib>Yang, Yang ; Canty, Allan J ; Richard A. J. O’Hair</creatorcontrib><description>The gas-phase extrusion–insertion (ExIn) reactions of the palladium complexes [(phen)nPd(O2SC6H5)]+ (phen = 1,10-phenanthroline, n = 1 or 2), were investigated in the gas phase by multistage mass spectrometry (MSn) experiments consisting of electrospray ionisation and a linear ion trap combined with density functional theory (DFT) calculations. Desulfination of palladium sulfinate cations under collision-induced dissociation (CID) generates the organopalladium intermediates [(phen)nPd(C6H5)]+. Of these two organometallic cations, only [(phen)Pd(C6H5)]+ reacts with phenyl isocyanate via insertion to yield [(phen)Pd(NPhC(O)C6H5)]+. The formation of a coordinated amidate anion is supported by DFT calculations. In exploring this reactivity in the solution phase, we found that heating a mixture of benzenesulfinic acid, phenylisocyanate and palladium trifluoroacetate under a range of different conditions (ligand free versus with ligand, different solvents, addition of acid or base) failed to lead to the formation N-phenyl-benzamide in all cases. Instead, biphenyl was formed and could be isolated in a yield of 46%. DFT calculations using a solvent continuum reveal that the barrier associated with the insertion reaction lies above the competing sequential reactions of desulfination of a second phenyl sulfinate followed by reductive elimination of biphenyl.</description><identifier>ISSN: 1529-5036</identifier><identifier>DOI: 10.1071/CH22209</identifier><language>eng</language><publisher>Collingwood: CSIRO</publisher><subject>Benzamide ; Cations ; Density functional theory ; Extrusion ; Insertion ; Isocyanates ; Ligands ; Mass spectrometry ; Palladium ; Solvents ; Vapor phases</subject><ispartof>Critical studies in media communication, 2023-01, Vol.76 (1), p.49</ispartof><rights>Copyright CSIRO 2023</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c216t-94529013cdf3c37084b50e2061667fe8033312c64b64bcbc793c473600f4cae93</citedby></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids></links><search><creatorcontrib>Yang, Yang</creatorcontrib><creatorcontrib>Canty, Allan J</creatorcontrib><creatorcontrib>Richard A. J. O’Hair</creatorcontrib><title>Why does the synthesis of N-phenylbenzamide from benzenesulfinate and phenylisocyanate via the palladium-mediated Extrusion–Insertion pathway not work? A mechanistic exploration</title><title>Critical studies in media communication</title><description>The gas-phase extrusion–insertion (ExIn) reactions of the palladium complexes [(phen)nPd(O2SC6H5)]+ (phen = 1,10-phenanthroline, n = 1 or 2), were investigated in the gas phase by multistage mass spectrometry (MSn) experiments consisting of electrospray ionisation and a linear ion trap combined with density functional theory (DFT) calculations. Desulfination of palladium sulfinate cations under collision-induced dissociation (CID) generates the organopalladium intermediates [(phen)nPd(C6H5)]+. Of these two organometallic cations, only [(phen)Pd(C6H5)]+ reacts with phenyl isocyanate via insertion to yield [(phen)Pd(NPhC(O)C6H5)]+. The formation of a coordinated amidate anion is supported by DFT calculations. In exploring this reactivity in the solution phase, we found that heating a mixture of benzenesulfinic acid, phenylisocyanate and palladium trifluoroacetate under a range of different conditions (ligand free versus with ligand, different solvents, addition of acid or base) failed to lead to the formation N-phenyl-benzamide in all cases. Instead, biphenyl was formed and could be isolated in a yield of 46%. DFT calculations using a solvent continuum reveal that the barrier associated with the insertion reaction lies above the competing sequential reactions of desulfination of a second phenyl sulfinate followed by reductive elimination of biphenyl.</description><subject>Benzamide</subject><subject>Cations</subject><subject>Density functional theory</subject><subject>Extrusion</subject><subject>Insertion</subject><subject>Isocyanates</subject><subject>Ligands</subject><subject>Mass spectrometry</subject><subject>Palladium</subject><subject>Solvents</subject><subject>Vapor phases</subject><issn>1529-5036</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><recordid>eNotj0tOwzAQhr0AiVIQV7DEOuBH4jQrVFWFVqpgA2JZOc5EcUnsEDu0YcUdOAo34iS4LdJI_zy--UeD0BUlN5Sk9Ha2YIyR7ASNaMKyKCFcnKFz5zaEEJExOkI_r9WACwsO-wqwG0wQpx22JX6M2grMUOdgPmWjC8BlZxu8L8GA6-tSG-kBS1PgI6mdVYM8ND-0PDi2sq5lofsmaqDQYVLg-c53vdPW_H59L42Dzoc8gL7aygEb6_HWdm93eIobUJU02nmtMOza2nZyz16g01LWDi7_dYxe7ufPs0W0enpYzqarSDEqfJTF4WdCuSpKrnhKJnGeEGBEUCHSEiaEc06ZEnEeQuUqzbiKUy4IKWMlIeNjdH30bTv73oPz643tOxNOrsMioymLKeN_InN0Fg</recordid><startdate>20230101</startdate><enddate>20230101</enddate><creator>Yang, Yang</creator><creator>Canty, Allan J</creator><creator>Richard A. J. O’Hair</creator><general>CSIRO</general><scope>7SR</scope><scope>8FD</scope><scope>JG9</scope></search><sort><creationdate>20230101</creationdate><title>Why does the synthesis of N-phenylbenzamide from benzenesulfinate and phenylisocyanate via the palladium-mediated Extrusion–Insertion pathway not work? A mechanistic exploration</title><author>Yang, Yang ; Canty, Allan J ; Richard A. J. O’Hair</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c216t-94529013cdf3c37084b50e2061667fe8033312c64b64bcbc793c473600f4cae93</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><topic>Benzamide</topic><topic>Cations</topic><topic>Density functional theory</topic><topic>Extrusion</topic><topic>Insertion</topic><topic>Isocyanates</topic><topic>Ligands</topic><topic>Mass spectrometry</topic><topic>Palladium</topic><topic>Solvents</topic><topic>Vapor phases</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Yang, Yang</creatorcontrib><creatorcontrib>Canty, Allan J</creatorcontrib><creatorcontrib>Richard A. J. O’Hair</creatorcontrib><collection>Engineered Materials Abstracts</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><jtitle>Critical studies in media communication</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Yang, Yang</au><au>Canty, Allan J</au><au>Richard A. J. O’Hair</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Why does the synthesis of N-phenylbenzamide from benzenesulfinate and phenylisocyanate via the palladium-mediated Extrusion–Insertion pathway not work? A mechanistic exploration</atitle><jtitle>Critical studies in media communication</jtitle><date>2023-01-01</date><risdate>2023</risdate><volume>76</volume><issue>1</issue><spage>49</spage><pages>49-</pages><issn>1529-5036</issn><abstract>The gas-phase extrusion–insertion (ExIn) reactions of the palladium complexes [(phen)nPd(O2SC6H5)]+ (phen = 1,10-phenanthroline, n = 1 or 2), were investigated in the gas phase by multistage mass spectrometry (MSn) experiments consisting of electrospray ionisation and a linear ion trap combined with density functional theory (DFT) calculations. Desulfination of palladium sulfinate cations under collision-induced dissociation (CID) generates the organopalladium intermediates [(phen)nPd(C6H5)]+. Of these two organometallic cations, only [(phen)Pd(C6H5)]+ reacts with phenyl isocyanate via insertion to yield [(phen)Pd(NPhC(O)C6H5)]+. The formation of a coordinated amidate anion is supported by DFT calculations. In exploring this reactivity in the solution phase, we found that heating a mixture of benzenesulfinic acid, phenylisocyanate and palladium trifluoroacetate under a range of different conditions (ligand free versus with ligand, different solvents, addition of acid or base) failed to lead to the formation N-phenyl-benzamide in all cases. Instead, biphenyl was formed and could be isolated in a yield of 46%. DFT calculations using a solvent continuum reveal that the barrier associated with the insertion reaction lies above the competing sequential reactions of desulfination of a second phenyl sulfinate followed by reductive elimination of biphenyl.</abstract><cop>Collingwood</cop><pub>CSIRO</pub><doi>10.1071/CH22209</doi><oa>free_for_read</oa></addata></record> |
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subjects | Benzamide Cations Density functional theory Extrusion Insertion Isocyanates Ligands Mass spectrometry Palladium Solvents Vapor phases |
title | Why does the synthesis of N-phenylbenzamide from benzenesulfinate and phenylisocyanate via the palladium-mediated Extrusion–Insertion pathway not work? A mechanistic exploration |
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