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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
Main Authors: Yang, Yang, Canty, Allan J, Richard A. J. O’Hair
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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.
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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%. 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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. 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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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source Taylor and Francis Social Sciences and Humanities Collection
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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