Comparison of thermodynamic and kinetic aspects of oxidative addition of PhE-EPh (E = S, Se, Te) to Mo(CO)3(PR3)2, W(CO)3(PR3)2, and Mo(N[tBu]Ar) 3 complexes. The role of oxidation state and ancillary ligands in metal complex induced chalcogenyl radical generation

James E. McDonough, John J. Weir, Kengkaj Sukcharoenphon, Carl Hoff, Olga P. Kryatova, Elena V. Rybak-Akimova, Brian L. Scott, Gregory J. Kubas, Arjun Mendiratta, Christopher C. Cummins

Research output: Contribution to journalArticle

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Abstract

Enthalpies of oxidative addition of PhE-EPh (E = S, Se, Te) to the M(0) complexes M(PiPr3)2- (CO)3 (M = Mo, W) to form stable complexes M(EPh)(Pir 3)2(CO)3 are reported and compared to analogous data for addition to the Mo(III) complexes Mo(N[tBu]Ar)3 (Ar = 3,5-C6H3Me2) to form diamagnetic Mo(IV) phenyl chalcogenide complexes Mo(N[tBu]Ar)3(EPh). Reactions are increasingly exothermic based on metal complex, Mo(P iPr3)2(CO)3 < W(P iPr3)2(CO)3 < Mo(N[ tBu]Ar)3, and in terms of chalcogenide, PhTe-TePh < PhSe-SePh < PhS-SPh. These data are used to calculate L0M-EPh bond strengths, which are used to estimate the energetics of production of a free EPh radical when a dichalcogenide interacts with a specific metal complex. To test these data, reactions of Mo(N[tBu]Ar) 3 and Mo(PiPr3)2(CO)3 with PhSe-SePh were studied by stopped-flow kinetics. First- and second-order dependence on metal ion concentration was determined for these two complexes, respectively, in keeping with predictions based on thermochemical data. ESR data are reported for the full set of bound chalcogenyl radical complexes (PhE )M(PiPr3)2(CO)3; g values increase on going from S to Se, to Te, and from Mo to W. Calculations of electron densities of the SOMO show increasing electron density on the chalcogen atom on going from S to Se to Te. The crystal structure of W( TePh)(PiPr3)2(CO)3 is reported.

Original languageEnglish
Pages (from-to)10295-10303
Number of pages9
JournalJournal of the American Chemical Society
Volume128
Issue number31
DOIs
StatePublished - Aug 9 2006
Externally publishedYes

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Coordination Complexes
Carbon Monoxide
Metal complexes
Thermodynamics
Carrier concentration
Ligands
Oxidation
Kinetics
Free radicals
Metal ions
Paramagnetic resonance
Enthalpy
Crystal structure
Atoms
Chalcogens
Electrons
Free Radicals
Metals
Ions

ASJC Scopus subject areas

  • Chemistry(all)

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Comparison of thermodynamic and kinetic aspects of oxidative addition of PhE-EPh (E = S, Se, Te) to Mo(CO)3(PR3)2, W(CO)3(PR3)2, and Mo(N[tBu]Ar) 3 complexes. The role of oxidation state and ancillary ligands in metal complex induced chalcogenyl radical generation. / McDonough, James E.; Weir, John J.; Sukcharoenphon, Kengkaj; Hoff, Carl; Kryatova, Olga P.; Rybak-Akimova, Elena V.; Scott, Brian L.; Kubas, Gregory J.; Mendiratta, Arjun; Cummins, Christopher C.

In: Journal of the American Chemical Society, Vol. 128, No. 31, 09.08.2006, p. 10295-10303.

Research output: Contribution to journalArticle

McDonough, James E. ; Weir, John J. ; Sukcharoenphon, Kengkaj ; Hoff, Carl ; Kryatova, Olga P. ; Rybak-Akimova, Elena V. ; Scott, Brian L. ; Kubas, Gregory J. ; Mendiratta, Arjun ; Cummins, Christopher C. / Comparison of thermodynamic and kinetic aspects of oxidative addition of PhE-EPh (E = S, Se, Te) to Mo(CO)3(PR3)2, W(CO)3(PR3)2, and Mo(N[tBu]Ar) 3 complexes. The role of oxidation state and ancillary ligands in metal complex induced chalcogenyl radical generation. In: Journal of the American Chemical Society. 2006 ; Vol. 128, No. 31. pp. 10295-10303.
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title = "Comparison of thermodynamic and kinetic aspects of oxidative addition of PhE-EPh (E = S, Se, Te) to Mo(CO)3(PR3)2, W(CO)3(PR3)2, and Mo(N[tBu]Ar) 3 complexes. The role of oxidation state and ancillary ligands in metal complex induced chalcogenyl radical generation",
abstract = "Enthalpies of oxidative addition of PhE-EPh (E = S, Se, Te) to the M(0) complexes M(PiPr3)2- (CO)3 (M = Mo, W) to form stable complexes M(•EPh)(Pir 3)2(CO)3 are reported and compared to analogous data for addition to the Mo(III) complexes Mo(N[tBu]Ar)3 (Ar = 3,5-C6H3Me2) to form diamagnetic Mo(IV) phenyl chalcogenide complexes Mo(N[tBu]Ar)3(EPh). Reactions are increasingly exothermic based on metal complex, Mo(P iPr3)2(CO)3 < W(P iPr3)2(CO)3 < Mo(N[ tBu]Ar)3, and in terms of chalcogenide, PhTe-TePh < PhSe-SePh < PhS-SPh. These data are used to calculate L0M-EPh bond strengths, which are used to estimate the energetics of production of a free •EPh radical when a dichalcogenide interacts with a specific metal complex. To test these data, reactions of Mo(N[tBu]Ar) 3 and Mo(PiPr3)2(CO)3 with PhSe-SePh were studied by stopped-flow kinetics. First- and second-order dependence on metal ion concentration was determined for these two complexes, respectively, in keeping with predictions based on thermochemical data. ESR data are reported for the full set of bound chalcogenyl radical complexes (PhE •)M(PiPr3)2(CO)3; g values increase on going from S to Se, to Te, and from Mo to W. Calculations of electron densities of the SOMO show increasing electron density on the chalcogen atom on going from S to Se to Te. The crystal structure of W( •TePh)(PiPr3)2(CO)3 is reported.",
author = "McDonough, {James E.} and Weir, {John J.} and Kengkaj Sukcharoenphon and Carl Hoff and Kryatova, {Olga P.} and Rybak-Akimova, {Elena V.} and Scott, {Brian L.} and Kubas, {Gregory J.} and Arjun Mendiratta and Cummins, {Christopher C.}",
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T1 - Comparison of thermodynamic and kinetic aspects of oxidative addition of PhE-EPh (E = S, Se, Te) to Mo(CO)3(PR3)2, W(CO)3(PR3)2, and Mo(N[tBu]Ar) 3 complexes. The role of oxidation state and ancillary ligands in metal complex induced chalcogenyl radical generation

AU - McDonough, James E.

AU - Weir, John J.

AU - Sukcharoenphon, Kengkaj

AU - Hoff, Carl

AU - Kryatova, Olga P.

AU - Rybak-Akimova, Elena V.

AU - Scott, Brian L.

AU - Kubas, Gregory J.

AU - Mendiratta, Arjun

AU - Cummins, Christopher C.

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N2 - Enthalpies of oxidative addition of PhE-EPh (E = S, Se, Te) to the M(0) complexes M(PiPr3)2- (CO)3 (M = Mo, W) to form stable complexes M(•EPh)(Pir 3)2(CO)3 are reported and compared to analogous data for addition to the Mo(III) complexes Mo(N[tBu]Ar)3 (Ar = 3,5-C6H3Me2) to form diamagnetic Mo(IV) phenyl chalcogenide complexes Mo(N[tBu]Ar)3(EPh). Reactions are increasingly exothermic based on metal complex, Mo(P iPr3)2(CO)3 < W(P iPr3)2(CO)3 < Mo(N[ tBu]Ar)3, and in terms of chalcogenide, PhTe-TePh < PhSe-SePh < PhS-SPh. These data are used to calculate L0M-EPh bond strengths, which are used to estimate the energetics of production of a free •EPh radical when a dichalcogenide interacts with a specific metal complex. To test these data, reactions of Mo(N[tBu]Ar) 3 and Mo(PiPr3)2(CO)3 with PhSe-SePh were studied by stopped-flow kinetics. First- and second-order dependence on metal ion concentration was determined for these two complexes, respectively, in keeping with predictions based on thermochemical data. ESR data are reported for the full set of bound chalcogenyl radical complexes (PhE •)M(PiPr3)2(CO)3; g values increase on going from S to Se, to Te, and from Mo to W. Calculations of electron densities of the SOMO show increasing electron density on the chalcogen atom on going from S to Se to Te. The crystal structure of W( •TePh)(PiPr3)2(CO)3 is reported.

AB - Enthalpies of oxidative addition of PhE-EPh (E = S, Se, Te) to the M(0) complexes M(PiPr3)2- (CO)3 (M = Mo, W) to form stable complexes M(•EPh)(Pir 3)2(CO)3 are reported and compared to analogous data for addition to the Mo(III) complexes Mo(N[tBu]Ar)3 (Ar = 3,5-C6H3Me2) to form diamagnetic Mo(IV) phenyl chalcogenide complexes Mo(N[tBu]Ar)3(EPh). Reactions are increasingly exothermic based on metal complex, Mo(P iPr3)2(CO)3 < W(P iPr3)2(CO)3 < Mo(N[ tBu]Ar)3, and in terms of chalcogenide, PhTe-TePh < PhSe-SePh < PhS-SPh. These data are used to calculate L0M-EPh bond strengths, which are used to estimate the energetics of production of a free •EPh radical when a dichalcogenide interacts with a specific metal complex. To test these data, reactions of Mo(N[tBu]Ar) 3 and Mo(PiPr3)2(CO)3 with PhSe-SePh were studied by stopped-flow kinetics. First- and second-order dependence on metal ion concentration was determined for these two complexes, respectively, in keeping with predictions based on thermochemical data. ESR data are reported for the full set of bound chalcogenyl radical complexes (PhE •)M(PiPr3)2(CO)3; g values increase on going from S to Se, to Te, and from Mo to W. Calculations of electron densities of the SOMO show increasing electron density on the chalcogen atom on going from S to Se to Te. The crystal structure of W( •TePh)(PiPr3)2(CO)3 is reported.

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