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

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

8 Citations (Scopus)

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	Comprehensive Inorganic Chemistry II
Subtitle of host publication	From Elements to Applications
Publisher	Elsevier
Pages	635-694
Number of pages	60
Volume	9
Edition	2
ISBN (Print)	9780080965291
DOIs	https://doi.org/10.1016/B978-0-08-097774-4.00929-3
Publication status	Published - 2013

Keywords

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

ASJC Scopus subject areas

General Chemistry

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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.\}",

year = "2013",

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booktitle = "Comprehensive Inorganic Chemistry II",

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T1 - Mechanistic Studies of CX Bond Activation at Transition-Metal Centers

AU - Algarra, A. G.

AU - MacGregor, S. A.

AU - Panetier, J. A.

PY - 2013

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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

UR - https://www.scopus.com/pages/publications/84902571850

U2 - 10.1016/B978-0-08-097774-4.00929-3

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

M3 - Chapter

AN - SCOPUS:84902571850

SN - 9780080965291

VL - 9

SP - 635

EP - 694

BT - Comprehensive Inorganic Chemistry II

PB - Elsevier

ER -

Mechanistic Studies of CX Bond Activation at Transition-Metal Centers

Abstract

Keywords

ASJC Scopus subject areas

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