Mechanistic Studies of CX Bond Activation at Transition-Metal Centers

A. G. Algarra; S. A. MacGregor; J. A. Panetier

doi:10.1016/B978-0-08-097774-4.00929-3

Mechanistic Studies of CX Bond Activation at Transition-Metal Centers

A. G. Algarra^*, S. A. MacGregor, J. A. Panetier

^*Corresponding author for this work

School of Chemistry

Research output: Chapter in Book/Report/Conference proceeding › Chapter

Abstract

This chapter surveys mechanistic computational studies on the activation of CX single bonds mediated by transition-metal centers. X can be based on any element of groups 13-17 and 'mechanistic' indicates that the transition state for CX bond activation has been located. Bond activation itself refers to the cleavage of a CX bond such that both partners may (potentially) act as neutral one-electron donors to the metal center. This definition covers oxidative addition, typically via a concerted and also by S_N2 or radical processes; also included are σ-bond metathesis, as well as CX cleavage promoted by Lewis acidic and Lewis basic species. The reactivity of neutral transition atoms and cations (often modeling gas-phase experimental reactivity) and of molecular complexes (of relevance to solution-phase reactivity and homogeneous catalysis) is discussed.

Original language	English
Title of host publication	Theory and Methods
Publisher	Elsevier Ireland Ltd
Pages	635-694
Number of pages	60
Volume	9
ISBN (Print)	9780080965291
DOIs	https://doi.org/10.1016/B978-0-08-097774-4.00929-3
Publication status	Published - Aug 2013

Keywords

Ab initio calculations
Bond activation
Cross-coupling
CX activation
Density functional theory
Homogeneous catalysis
Kinetics
Mechanism
Reactivity
Thermodynamics
Transition metals

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10.1016/B978-0-08-097774-4.00929-3

Cite this

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title = "Mechanistic Studies of CX Bond Activation at Transition-Metal Centers",

abstract = "This chapter surveys mechanistic computational studies on the activation of CX single bonds mediated by transition-metal centers. X can be based on any element of groups 13-17 and 'mechanistic' indicates that the transition state for CX bond activation has been located. Bond activation itself refers to the cleavage of a CX bond such that both partners may (potentially) act as neutral one-electron donors to the metal center. This definition covers oxidative addition, typically via a concerted and also by SN2 or radical processes; also included are σ-bond metathesis, as well as CX cleavage promoted by Lewis acidic and Lewis basic species. The reactivity of neutral transition atoms and cations (often modeling gas-phase experimental reactivity) and of molecular complexes (of relevance to solution-phase reactivity and homogeneous catalysis) is discussed.",

keywords = "Ab initio calculations, Bond activation, Cross-coupling, CX activation, Density functional theory, Homogeneous catalysis, Kinetics, Mechanism, Reactivity, Thermodynamics, Transition metals",

author = "Algarra, {A. G.} and MacGregor, {S. A.} and Panetier, {J. A.}",

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AU - MacGregor, S. A.

AU - Panetier, J. A.

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N2 - This chapter surveys mechanistic computational studies on the activation of CX single bonds mediated by transition-metal centers. X can be based on any element of groups 13-17 and 'mechanistic' indicates that the transition state for CX bond activation has been located. Bond activation itself refers to the cleavage of a CX bond such that both partners may (potentially) act as neutral one-electron donors to the metal center. This definition covers oxidative addition, typically via a concerted and also by SN2 or radical processes; also included are σ-bond metathesis, as well as CX cleavage promoted by Lewis acidic and Lewis basic species. The reactivity of neutral transition atoms and cations (often modeling gas-phase experimental reactivity) and of molecular complexes (of relevance to solution-phase reactivity and homogeneous catalysis) is discussed.

AB - This chapter surveys mechanistic computational studies on the activation of CX single bonds mediated by transition-metal centers. X can be based on any element of groups 13-17 and 'mechanistic' indicates that the transition state for CX bond activation has been located. Bond activation itself refers to the cleavage of a CX bond such that both partners may (potentially) act as neutral one-electron donors to the metal center. This definition covers oxidative addition, typically via a concerted and also by SN2 or radical processes; also included are σ-bond metathesis, as well as CX cleavage promoted by Lewis acidic and Lewis basic species. The reactivity of neutral transition atoms and cations (often modeling gas-phase experimental reactivity) and of molecular complexes (of relevance to solution-phase reactivity and homogeneous catalysis) is discussed.

KW - Ab initio calculations

KW - Bond activation

KW - Cross-coupling

KW - CX activation

KW - Density functional theory

KW - Homogeneous catalysis

KW - Kinetics

KW - Mechanism

KW - Reactivity

KW - Thermodynamics

KW - Transition metals

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SN - 9780080965291

VL - 9

SP - 635

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BT - Theory and Methods

PB - Elsevier Ireland Ltd

ER -

Mechanistic Studies of CX Bond Activation at Transition-Metal Centers

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Keywords

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