Combined Experimental and Computational Investigation of the Mechanism of Nickel-Catalyzed Three-Component Addition Processes

Hratchian, Hrant P.; Chowdhury, Sanjoy K.; Gutiérrez-Garcı́a, Vı́ctor Manuel; Amarasinghe, Kande K. D.; Heeg, Mary Jane; Schlegel, H. Bernhard; Montgomery, John

doi:10.1021/om049471a

Cited by 111 publications

(62 citation statements)

References 93 publications

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“…The lengths of the NiO and NiC bonds suggest that the interaction is not symmetrical, and can be considered closer to η 2 ‐CO than a η 3 ‐pseudoallylic interaction. The relatively long C${\overline {\hbox {-} \hbox {-}}}$ O and short C${\overline {\hbox {-} \hbox {-}}}$ C bonds further support this view; hence, an early transition state in the O→C reaction coordinate is indicated 19. The energy difference between TS and O ‐Ni (ca.…”

Section: Resultsmentioning

confidence: 76%

Cyclic Enolates of Ni and Pd: Equilibrium between C‐ and O‐Bound Tautomers and Reactivity Studies

Cámpora¹,

Maya²,

Carmona³

et al. 2005

Chemistry A European J

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2-acylaryl complexes of Ni and Pd containing chelating diphosphines react with KtBuO to give metallacyclic enolate complexes. While coordination through the carbon atom is preferred in the case of Pd, the nickel O-enolate compounds are formed as the corresponding O-tautomers. Slow equilibration between O- and C-enolate tautomers is observed for the nickel complex with an unsubstituted enolate function (M-O-C=CH(2)). Theoretical DFT calculations suggest that the barrier for the tautomer exchange has its origin in the rigidity of the metallacycle. Whilst the C-enolate tautomer is unreactive towards aldehydes, the corresponding O-enolate adds to MeCHO and PhCHO, giving rise to products that retain the enolate functionality. The carbonylation of these products cleanly leads to the formation of enol lactones in a highly selective manner.

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Section: Resultsmentioning

confidence: 76%

Cyclic Enolates of Ni and Pd: Equilibrium between C‐ and O‐Bound Tautomers and Reactivity Studies

Cámpora¹,

Maya²,

Carmona³

et al. 2005

Chemistry A European J

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“…234 A number of these processes involve as a third component a main group organometallic entity. 235 In this area, two recent studies from the groups of Schlegel and Montgomery (Scheme 40) 236 and Ogoshi and Kurosawa 237 deal with the role of ZnMe2 and AlMe3, respectively, in promoting the oxidative cyclization reaction. In both cases a bridging μ-CH3 intermediate between Ni and either Zn or Al was suggested (i. e. 3.34 in Scheme 40).…”

Section: Tm-ch3 As Intermediates In Catalysismentioning

confidence: 99%

Methyl Complexes of the Transition Metals

Campos

López‐Serrano

Peloso

et al. 2016

Chemistry A European J

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Organometallic chemistry can be considered as a wide area of knowledge that combines concepts of classic organic chemistry, i.e. based essentially on carbon, with molecular inorganic chemistry, especially with coordination compounds. Transition metal methyl complexes probably represent the simplest and most fundamental way to view how these two major areas of chemistry combine and merge into novel species with intriguing features in terms of reactivity, structure, and bonding. Citing more than 500 bibliographic references, this review aims to offer a concise view of recent advances in the field of transition metal complexes containing M-CH3 fragments. Taking into account the impressive amount of data that are continuously provided by organometallic chemists in this area, this review is mainly focused on results of the last 5 years. After a panoramic overview on M-CH3 compounds of groups 3 to 11 which includes the most recent landmark findings in this area, two further sections are dedicated to methyl-bridged complexes and reactivity.

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“…This reaction has been studied extensively experimentally by Montgomery and co-workers, 43 and has recently been further investigated in a combined experimental and computational work. 44 The energy profile as a function of reaction coordinate using LQA and HPC is shown in Fig. 4.…”

Section: F Nickel Metallacycle Formation Reactionmentioning

confidence: 99%

Accurate reaction paths using a Hessian based predictor–corrector integrator

Hratchian

Schlegel²

2004

The Journal of Chemical Physics

Self Cite

840

541

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Central to the theoretical description of a chemical reaction is the reaction pathway. The intrinsic reaction coordinate is defined as the steepest descent path in mass weighted Cartesian coordinates that connects the transition state to reactants and products. In this work, a new integrator for the steepest descent pathway is presented. This method is a Hessian based predictor-corrector algorithm that affords pathways comparable to our previous fourth order method at the cost of a second order approach. The proposed integrator is tested on an analytic surface, four moderately sized chemical reactions, and one larger organometallic system.

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Combined Experimental and Computational Investigation of the Mechanism of Nickel-Catalyzed Three-Component Addition Processes

Cited by 111 publications

References 93 publications

Cyclic Enolates of Ni and Pd: Equilibrium between C‐ and O‐Bound Tautomers and Reactivity Studies

Cyclic Enolates of Ni and Pd: Equilibrium between C‐ and O‐Bound Tautomers and Reactivity Studies

Methyl Complexes of the Transition Metals

Accurate reaction paths using a Hessian based predictor–corrector integrator

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