Methane exchange reactions of lanthanide and early-transition-metal methyl complexes

“…Watson first reported in 1983 that Cp* 2 LuMe underwent exchange with 13 CH 4 , in cyclohexane solvent, indicating that the preference for activation of less substituted hydrocarbons extended beyond simple electrophilic and oxidative additions (141,142). Certainly this selectivity could be viewed simply as another manifestation of the relatively greater metal-R bond strengths of lesssubstituted alkyls.…”

Section: Sigma-bond Metathesismentioning

confidence: 99%

Organometallic C—H Bond Activation: An Introduction

Goldman¹,

Goldberg²

2004

ACS Symposium Series

113

View full text Add to dashboard Cite

An introduction to the field of activation and fimctionalization of C-H bonds by solution-phase transition -metal-based systems is presented, with an emphasis on the activation of aliphatic C-H bonds. The focus of this chapter is on stoichiometric and catalytic reactions that operate via organometallic mechanisms, i.e., those in which a bond is formed between the metal center and the carbon undergoing reactionThe carbon-hydrogen bond is the un-functional group. Its unique position in organic chemistry is well illustrated by the standard representation of organic molecules: the presence of C-H bonds is indicated simply by the absence of any other bond. This "invisibility" of C-H bonds reflects both their ubiquitous nature and their lack of reactivity. With these characteristics in mind it is clear that if the ability to selectively fiinctionalize C-H bonds were well developed, it could potentially constitute the most broadly applicable and powerful class of transformations in organic synthesis. Realization of such potential could revolutionize the synthesis of organic molecules ranging in complexity from methanol to the most elaborate natural or unnatural products.The following chapters in this volume offer a view of many of the current leading research efforts in this field, in particular those focused on the activation

show abstract

“…The intermolecular activation of CÀH bonds is a highly desirable process [1][2][3][4][5][6][7][8] and is part of many catalytic systems, [9][10][11] for example, the dehydrogenation of alkanes to alkenes. [12][13][14] Detailed studies by various groups clearly established that the CÀH activation process is under kinetic rather than thermodynamic control in most cases.…”

Section: Dedicated To Professor Robert G Bergman On the Occasion Of mentioning

confidence: 99%

“…Overall, the outcome of the CÀH activation reaction resembles a s-bond metathesis process, which is the anticipated mechanism for d 0 early-transition-metal and lanthanide row complexes. [8,18,19] For d n -configured complexes with n ! 2 there are other mechanistic alternatives, for example, a CÀH oxidative-addition step, followed by CÀH reductive elimination.…”

Section: Dedicated To Professor Robert G Bergman On the Occasion Of mentioning

confidence: 99%

Transition‐Metal Complexes with Sterically Demanding Ligands: Facile Thermal Intermolecular CH Bond Activation in a Square‐Planar Ir^I Complex

Nückel

Burger

2003

Angew Chem Int Ed

View full text Add to dashboard Cite

show abstract

Methane exchange reactions of lanthanide and early-transition-metal methyl complexes

Cited by 383 publications

References 2 publications

Computational study of methane activation by mercury(II) complexes

Computational study of methane activation by mercury(II) complexes

Organometallic C—H Bond Activation: An Introduction

Transition‐Metal Complexes with Sterically Demanding Ligands: Facile Thermal Intermolecular CH Bond Activation in a Square‐Planar Ir^I Complex

Contact Info

Product

Resources

About

Methane exchange reactions of lanthanide and early-transition-metal methyl complexes

Cited by 383 publications

References 2 publications

Computational study of methane activation by mercury(II) complexes

Computational study of methane activation by mercury(II) complexes

Organometallic C—H Bond Activation: An Introduction

Transition‐Metal Complexes with Sterically Demanding Ligands: Facile Thermal Intermolecular CH Bond Activation in a Square‐Planar IrI Complex

Contact Info

Product

Resources

About

Transition‐Metal Complexes with Sterically Demanding Ligands: Facile Thermal Intermolecular CH Bond Activation in a Square‐Planar Ir^I Complex