Metal control of selectivity in acetate-assisted C–H bond activation: an experimental and computational study of heterocyclic, vinylic and phenylic C(sp<sup>2</sup>)–H bonds at Ir and Rh

Carr, Kevin J. T.; Davies, David; Macgregor, Stuart A.; Singh, Kuldip; Villa‐Marcos, Barbara

doi:10.1039/c4sc00738g

Cited by 47 publications

(36 citation statements)

References 37 publications

(8 reference statements)

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“…545,546 On the basis of DFT computations at the PCM (methanol) B3LYP/6-31G(d,p)-(LANL2DZ) level of theory, the higher reactivity of Ir compared to Rh was attributed to its higher electrophilicity which facilitates C−H activation both kinetically as well as thermodynamically.…”

Section: Allylic Substitutionmentioning

confidence: 99%

Computational Studies of Synthetically Relevant Homogeneous Organometallic Catalysis Involving Ni, Pd, Ir, and Rh: An Overview of Commonly Employed DFT Methods and Mechanistic Insights

et al. 2015

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Section: Allylic Substitutionmentioning

confidence: 99%

Computational Studies of Synthetically Relevant Homogeneous Organometallic Catalysis Involving Ni, Pd, Ir, and Rh: An Overview of Commonly Employed DFT Methods and Mechanistic Insights

et al. 2015

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“…This involves the Ru-bound oxygen atom and a four-membered (i.e., AMLA-4) transition state. More recently, Davies, Macgregor, and coworkers highlighted the importance of dispersion effects when seeking a more quantitative assessment of observed data [61]. Experimentally , consistent with an irreversible reaction under kinetic control.…”

Section: Intramolecular Heteroatom-assisted C-h Activationmentioning

confidence: 99%

“…Computed data (kcal mol −1 )give the overall free energy changes, ΔG calc , for M = Rh and calculated activation barriers, ΔG ‡ calc , for M = Ir[61].…”

mentioning

confidence: 99%

Computational Studies of Heteroatom‐Assisted CH Activation at Ru, Rh, Ir, and Pd as a Basis for Heterocycle Synthesis and Derivatization

Carr¹,

Macgregor²,

McMullin³

2016

Transition Metal‐Catalyzed Heterocycle Synthesis via CH Activation

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IntroductionModern computational chemistry is a key tool by which insight into organometallic reaction mechanisms can be gained. The ability to characterize short-lived intermediates and transition states provides an ideal complement to experiment, where such information is often extremely difficult, if not impossible, to obtain. Recent years have seen great advances in understanding the mechanisms of C-H bond activation, and this area was the subject of several major reviews toward the end of the last decade [1,2]. More recently, the focus has shifted to how C-H activation can be integrated into catalytic cycles for useful organic transformations. The C-H bond activation event is itself mechanistically diverse, with oxidative addition (OA), σ-bond metathesis (SBM), and electrophilic activation (EA) all potentially available at late transition metal centers, depending on the metal, its oxidation state, and the coordination environment. C-H activation assisted by a heteroatom base (typically a carboxylate or carbonate) falls into the last of these categories and forms the focus of this chapter. More recently, computational studies of catalytic cycles for C-H activation and functionalization have become more common. These reveal the complexity of what are usually multiple-step processes, and calculations are particularly well placed to test different mechanistic possibilities. Such studies are most effectively pursued through a close interaction between experiment and computation, and increasingly this is allowing for a more quantitative assessment of computed reaction mechanisms.As well as progress in mechanistic understanding, the last 10 years have seen important developments in the computational methodologies available to model transition metal reactivity. While density functional theory (DFT) remains the core method of choice, the ability to model larger systems that more closely reflect experiment has highlighted the known shortcomings of DFT in describing dispersion interactions. These long-range, stabilizing interactions are individually weak, but their cumulative effect in large systems can be significant. Methods to incorporate this component include its separate calculation (e.g., Transition Metal-Catalyzed Heterocycle Synthesis via C-H Activation, First Edition. Edited by Xiao-Feng Wu.

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“…The importance of treating dispersion effects was highlighted in a study by Davies, Macgregor and co-workers on the relative reactivity of C(sp 2 )-H bonds in N-alkylimines (H-L 1-5 ) and 2-phenylpyridine (H-L 6 ) at [MCl 2 Cp*] 2 dimers (M ¼ Rh, Ir) [15]. In the presence of NaOAc, these substrates give well-defined cyclometalated species as their chloride adducts, indicating that these reactions are all thermodynamically accessible (Scheme 1).…”

Section: Activation Of C(sp 2 )-H Bondsmentioning

confidence: 98%

Computational Studies on Heteroatom-Assisted C–H Activation and Functionalisation at Group 8 and 9 Metal Centres

Carr

Macgregor

McMullin

2015

C-H Bond Activation and Catalytic Functionalization I

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This chapter surveys computational studies on heteroatom-assisted C-H activation at group 8 and 9 metal centres and will cover the literature since 2009. The chapter first considers work where the mechanism of the C-H activation step is the primary concern and categorizes these into intramolecular (with directing groups) and intermolecular processes. Studies on C-H activation and functionalization will be presented, classified in terms of the nature of the functionalization process (oxidative coupling to form heterocycles, alkenylation and amination).

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Metal control of selectivity in acetate-assisted C–H bond activation: an experimental and computational study of heterocyclic, vinylic and phenylic C(sp²)–H bonds at Ir and Rh

Abstract: Experimental and DFT studies show the selectivity of C–H bond activation at [MCl2Cp*]2 (M = Ir, Rh) species can be controlled by the choice of metal catalyst, reflecting kinetic control at M = Ir and thermodynamic control at M = Rh.

Cited by 47 publications

References 37 publications

Computational Studies of Synthetically Relevant Homogeneous Organometallic Catalysis Involving Ni, Pd, Ir, and Rh: An Overview of Commonly Employed DFT Methods and Mechanistic Insights

Computational Studies of Synthetically Relevant Homogeneous Organometallic Catalysis Involving Ni, Pd, Ir, and Rh: An Overview of Commonly Employed DFT Methods and Mechanistic Insights

Computational Studies of Heteroatom‐Assisted CH Activation at Ru, Rh, Ir, and Pd as a Basis for Heterocycle Synthesis and Derivatization

Computational Studies on Heteroatom-Assisted C–H Activation and Functionalisation at Group 8 and 9 Metal Centres

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Metal control of selectivity in acetate-assisted C–H bond activation: an experimental and computational study of heterocyclic, vinylic and phenylic C(sp2)–H bonds at Ir and Rh

Abstract: Experimental and DFT studies show the selectivity of C–H bond activation at [MCl2Cp*]2 (M = Ir, Rh) species can be controlled by the choice of metal catalyst, reflecting kinetic control at M = Ir and thermodynamic control at M = Rh.

Cited by 47 publications

References 37 publications

Computational Studies of Synthetically Relevant Homogeneous Organometallic Catalysis Involving Ni, Pd, Ir, and Rh: An Overview of Commonly Employed DFT Methods and Mechanistic Insights

Computational Studies of Synthetically Relevant Homogeneous Organometallic Catalysis Involving Ni, Pd, Ir, and Rh: An Overview of Commonly Employed DFT Methods and Mechanistic Insights

Computational Studies of Heteroatom‐Assisted CH Activation at Ru, Rh, Ir, and Pd as a Basis for Heterocycle Synthesis and Derivatization

Computational Studies on Heteroatom-Assisted C–H Activation and Functionalisation at Group 8 and 9 Metal Centres

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Metal control of selectivity in acetate-assisted C–H bond activation: an experimental and computational study of heterocyclic, vinylic and phenylic C(sp²)–H bonds at Ir and Rh