Net Oxidative Addition of H2 to {MII}2+ (M = Pd, Pt) by Heterolysis and Protic Rebound

Nisha Rao; Jonathan L. Kuo

doi:10.1021/jacs.5c07140

Net Oxidative Addition of H₂ to {M^II}²⁺ (M = Pd, Pt) by Heterolysis and Protic Rebound

Nisha Rao, Jonathan L. Kuo

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Electrophilic transition metal complexes like {M^II(EtXantphos)₂}²⁺ (M^II = Pd^II, Pt^II) heterolyze H₂ into a hydride-associated electrophile {H-M^II(EtXantphos)₂}⁺ and a proton, which typically associates to an added base (or basic ligand). For {H-M^II(EtXantphos)₂}⁺, the metal can be the most basic site in the system, which results in a product that is indistinguishable from oxidative addition {(H)₂M^IV(EtXantphos)₂}²⁺. By considering the kinetics and thermodynamics of each elementary step - initial heterolysis, followed by a subsequent return of the heterolyzed proton - we suggest that oxidative addition products may be underrepresented tautomers in heterolytic pathways.

Original language	English (US)
Pages (from-to)	22351-22357
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	147
Issue number	26
DOIs	https://doi.org/10.1021/jacs.5c07140
State	Published - Jul 2 2025

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "Net Oxidative Addition of H2 to \{MII\}2+ (M = Pd, Pt) by Heterolysis and Protic Rebound",

abstract = "Electrophilic transition metal complexes like \{MII(EtXantphos)2\}2+ (MII = PdII, PtII) heterolyze H2 into a hydride-associated electrophile \{H-MII(EtXantphos)2\}+ and a proton, which typically associates to an added base (or basic ligand). For \{H-MII(EtXantphos)2\}+, the metal can be the most basic site in the system, which results in a product that is indistinguishable from oxidative addition \{(H)2MIV(EtXantphos)2\}2+. By considering the kinetics and thermodynamics of each elementary step - initial heterolysis, followed by a subsequent return of the heterolyzed proton - we suggest that oxidative addition products may be underrepresented tautomers in heterolytic pathways.",

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T1 - Net Oxidative Addition of H2 to {MII}2+ (M = Pd, Pt) by Heterolysis and Protic Rebound

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AU - Kuo, Jonathan L.

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N2 - Electrophilic transition metal complexes like {MII(EtXantphos)2}2+ (MII = PdII, PtII) heterolyze H2 into a hydride-associated electrophile {H-MII(EtXantphos)2}+ and a proton, which typically associates to an added base (or basic ligand). For {H-MII(EtXantphos)2}+, the metal can be the most basic site in the system, which results in a product that is indistinguishable from oxidative addition {(H)2MIV(EtXantphos)2}2+. By considering the kinetics and thermodynamics of each elementary step - initial heterolysis, followed by a subsequent return of the heterolyzed proton - we suggest that oxidative addition products may be underrepresented tautomers in heterolytic pathways.

AB - Electrophilic transition metal complexes like {MII(EtXantphos)2}2+ (MII = PdII, PtII) heterolyze H2 into a hydride-associated electrophile {H-MII(EtXantphos)2}+ and a proton, which typically associates to an added base (or basic ligand). For {H-MII(EtXantphos)2}+, the metal can be the most basic site in the system, which results in a product that is indistinguishable from oxidative addition {(H)2MIV(EtXantphos)2}2+. By considering the kinetics and thermodynamics of each elementary step - initial heterolysis, followed by a subsequent return of the heterolyzed proton - we suggest that oxidative addition products may be underrepresented tautomers in heterolytic pathways.

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Net Oxidative Addition of H₂ to {M^II}²⁺ (M = Pd, Pt) by Heterolysis and Protic Rebound

Abstract

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