Theoretical Studies on the Metathesis Processes, [Tp(PH3)MR(η2‐HCH3)] → [Tp(PH3)M(CH3)(η2‐HR)] (M=Fe, Ru, and Os; R=H and CH3)

Lam, Wai Han; Jia, Guochen; Lin, Zhenyang; Lau, Chak Po; Eisenstein, Odile

doi:10.1002/chem.200204570

Cited by 69 publications

(71 citation statements)

References 67 publications

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“…In a subsequent paper, Lam et al compare the behavior of Fe, Ru, and Os in the metathesis processes shown in Equation (5) (M = Fe(Tp)(PH 3 ), Ru(Tp)(PH 3 ), Os(Tp)(PH 3 )) via DFT calculations. [88] ½MH þ CH 4 …”

Section: Mh(ch 2 R) Via M(h 2 -H-ch 2 R)mentioning

confidence: 99%

The σ‐CAM Mechanism: σ Complexes as the Basis of σ‐Bond Metathesis at Late‐Transition‐Metal Centers

2007

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Complexes in which a sigma-H--E bond (E=H, B, Si, C) acts as a two-electron donor to the metal center are called sigma complexes. Clues that it is possible to interconvert sigma ligands without a change in oxidation state derive from C--H activation reactions effecting isotope exchange and from dynamic rearrangements of sigma complexes (see Frontispiece). Through these pathways, metathesis of M--E bonds can occur at late transition metals. We call this process sigma-complex-assisted metathesis, or sigma-CAM, which is distinct from the familiar sigma-bond metathesis (typical for d(0) metals and requiring no intermediate) and from oxidative-reductive elimination mechanisms (inherently requiring intermediates with changed oxidation states and sometimes involving sigma complexes). There are examples of sigma-CAM mechanisms in catalysis, especially for alkane borylation and isotope exchange of alkanes. It may also occur in silylation and alkene hydrogenation.

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Section: Mh(ch 2 R) Via M(h 2 -H-ch 2 R)mentioning

confidence: 99%

The σ‐CAM Mechanism: σ Complexes as the Basis of σ‐Bond Metathesis at Late‐Transition‐Metal Centers

2007

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“…2). 16 Even more striking was the changing nature of the C-H activation process. With M = Os 'normal' 3-centred oxidative addition was characterised, but with the Ru and Fe analogues 4-centred transition states were seen.…”

Section: Sbm At L N M-r Bonds (R = Alkyl or Aryl)mentioning

confidence: 99%

Mechanisms of C–H bond activation: rich synergy between computation and experiment

et al. 2009

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Image reproduced with permission of Christophe CoperetPapers published in this issue include:A combined picture from theory and experiments on water oxidation, oxygen reduction and proton pumping Per E. M. Siegbahn and Margareta R. A. Blomberg, Dalton Trans., 2009, DOI: 10.1039 Recent computational studies of C-H bond activation at late transition metal systems are discussed and processes where lone pair assistance via heteroatom co-ligands or carboxylates are highlighted as a particularly promising means of cleaving C-H bonds. The term 'ambiphilic metal ligand activation' (AMLA) is introduced to describe such reactions.

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“…Intermediate between these extremes is a composite of the two transition states where the end result is a σ-bond metathesis mechanisms, but the metal is highly involved in bonding to the hydrogen in the transition state. This type of composite transition state has several names for nuanced versions, such as oxidatively added transition state (OATS) [50,51], metal-assisted σ-bond metathesis (MAσBM) [52,53], or σ-complex assisted metathesis (σ-CAM) [54]. Hall and Vastine [55] have shown that using atoms-inmolecules analysis provides a framework to understand the entire set of transition states along this mechanistic continuum.…”

Section: Cr King Et Almentioning

confidence: 99%

The Electronics of CH Activation by Energy Decomposition Analysis: From Transition Metals to Main-Group Metals

King

Gustafson

Ess

2015

Structure and Bonding

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Alkane CH activation is a fundamental reaction class where a metalligand complex reacts with a CH bond to give a metal-alkyl organometallic intermediate. CH activation reactions have been reported for a variety of transition metals and main-group metals. This chapter highlights recent quantum-mechanical studies that have used energy decomposition analysis (EDA) to provide insight into σ-coordination complexes and transition states for alkane CH activation reactions. These studies have provided new conceptual understanding of CH activation reactions and detailed insight into the physical nature and magnitude of interaction between alkanes with transition metals and main-group metals.

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Theoretical Studies on the Metathesis Processes, [Tp(PH₃)MR(η²‐HCH₃)] → [Tp(PH₃)M(CH₃)(η²‐HR)] (M=Fe, Ru, and Os; R=H and CH₃)

Cited by 69 publications

References 67 publications

The σ‐CAM Mechanism: σ Complexes as the Basis of σ‐Bond Metathesis at Late‐Transition‐Metal Centers

The σ‐CAM Mechanism: σ Complexes as the Basis of σ‐Bond Metathesis at Late‐Transition‐Metal Centers

Mechanisms of C–H bond activation: rich synergy between computation and experiment

The Electronics of CH Activation by Energy Decomposition Analysis: From Transition Metals to Main-Group Metals

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