Journal ArticleDOI
Relative bond dissociation energies for early transition metal alkyl, aryl, alkynyl and hydride compounds. Equilibration of metallated cyclopentadienyl derivatives of peralkylated hafnocene and scandocene with hydrocarbons and dihydrogen
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In this article, the relative bond dissociation energies (BDEs) have been obtained by equilibrating early transition metal alkyls and hydrides with H2 or the CH bonds of hydrocarbons.About:
This article is published in Polyhedron.The article was published on 1988-01-01. It has received 50 citations till now. The article focuses on the topics: Transition metal hydride & Cyclopentadienyl complex.read more
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Journal ArticleDOI
The Essential Role of Bond Energetics in C-H Activation/Functionalization.
TL;DR: The present review provides examples that applied the concept and values of C-H bond energy in rationalizing the observations associated with reactivity and/or selectivity in C- H activation/functionalization.
Book ChapterDOI
The Bonding of Metal-Alkynyl Complexes
TL;DR: In this paper, the best and simplest way of placing the M-C bond distances of metal-alkyl complexes in a context that allows insight into whether or not they manifest M-CCR π-interactions is to compare them to M−C bond distance of complexes where such effects are expected to be insignificant, as for metal−alkynyl compounds.
Journal ArticleDOI
Selectivities in Hydrocarbon Activation: Kinetic and Thermodynamic Investigations of Reversible 1,2-RH-Elimination from (silox)2(tBu3SiNH)TiR (silox = tBu3SiO)
TL;DR: In this article, a first-order process for 1,2-RH/D-elimination from 2-R was shown to achieve 24.8 °C in the presence of C2H4, butadiene, HC2H, and HC2tBu.
Journal ArticleDOI
Homogeneous Catalysis with Methane. A Strategy for the Hydromethylation of Olefins Based on the Nondegenerate Exchange of Alkyl Groups and σ-Bond Metathesis at Scandium
Aaron D. Sadow,T. Don Tilley +1 more
TL;DR: Kinetic studies revealed that the metalation of methane proceeds exclusively via a second-order pathway described by the rate law, and high selectivity toward methane activation suggested the participation of this chemistry in a catalytic hydromethylation, which was observed in the slow, Cp*(2)ScMe-catalyzed addition of methane across the double bond of propene to form isobutane.
Journal ArticleDOI
Synthesis and Characterization of Scandium Silyl Complexes of the Type Cp*2ScSiHRR‘. σ-Bond Metathesis Reactions and Catalytic Dehydrogenative Silation of Hydrocarbons
Aaron D. Sadow,T. Don Tilley +1 more
TL;DR: Study of scandium dihydrosilyl complexes in the context of hydrocarbon activation led to discovery of catalytic processes for the dehydrogenative silation of hydrocarbons (including methane, isobutene and cyclopropane) with Ph( 2)SiH(2) via sigma-bond metathesis.
References
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Journal ArticleDOI
Hydrocarbon Bond Dissociation Energies
TL;DR: The best available values for homolytic bond dissociation energies (BDEs) of various classes of neutral compounds are considered in a review as mentioned in this paper, focusing on prototypical radicals whose heats of formation, formerly thought to be well in hand, have recently been called into serious question.
Journal ArticleDOI
.sigma.-Bond metathesis for carbon-hydrogen bonds of hydrocarbons and Sc-R (R = H, alkyl, aryl) bonds of permethylscandocene derivatives. Evidence for noninvolvement of the .pi. system in electrophilic activation of aromatic and vinylic C-H bonds
Mark E. Thompson,Mark E. Thompson,Steven M. Baxter,A. Ray Bulls,Barbara J. Burger,Michael C. Nolan,Bernard D. Santarsiero,William P. Schaefer,John E. Bercaw +8 more
TL;DR: In this article, a structural analysis of hydride and hydrocarbyl derivatives of permethylscandocene has been carried out, and the possibility of involvement of the π-bond system in electrophilic activation of aromatic and vinylic C-H bonds has been examined.
Journal ArticleDOI
Relative metal-hydrogen, -oxygen, -nitrogen, and -carbon bond strengths for organoruthenium and organoplatinum compounds; equilibrium studies of Cp*(PMe3)2RuX and (DPPE)MePtX systems
TL;DR: A series of ruthenium, Cp*(PMe/sub 3/)/sub 2/RuX (Cp* = eta/sup 5/-C/sub 5/Me/Sub 5/), and platinum compounds have been prepared.
Journal ArticleDOI
Activation of alkanes with organotransition metal complexes.
TL;DR: Evidence has been obtained that this C-H insertion, or oxidative addition, reaction proceeds through a simple three-center transition state and does not involve organic free radicals as intermediates, providing an incentive for reexamining the factors that have been assumed to control the rate of reaction of transition metal complexes with C-h bonds.
Journal ArticleDOI
The mechanism and thermodynamics of alkane and arene carbon-hydrogen bond activation in (C5Me5)Rh(PMe3)(R)H
William D. Jones,Frank J. Feher +1 more
TL;DR: In this article, first-order reductive elimination was used to obtain a 5.4:1 selectivity for benzene over cyclopentane in a competition experiment at -35/sup 0/C. Mechanistic studies revealed a (1,2)-shift pathway around the ring with..delta..H/sup +/ =16.3 +/- 0.2
Related Papers (5)
Organometallic thermochemistry. Metal hydrocarbyl, hydride, halide, carbonyl, amide, and alkoxide bond enthalpy relationships and their implications in pentamethylcyclopentadienyl and cyclopentadienyl complexes of zirconium and hafnium
Laurel E. Schock,Tobin J. Marks +1 more