Nuclear magnetic resonance evidence for .pi.-&gt; sigma ligand conversion in platinum(II) complexes

Kaplan, Phyllis D.; Schmidt, Paul; Orchin, Milton

doi:10.1021/ja01017a056

Cited by 55 publications

(31 citation statements)

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“…[82] The selective Markovnikov hydroamination of 1-hexene [Eq. (19)] is significant, as rapid Pt-catalyzed olefin isomerization is common, and was observed by Tilley and coworkers. [77] Although the precise reason for the benefit of nBu 4 PBr as solvent is unknown, the high concentration of bromide ions in the reaction medium seems important as reactions in nBu 4 PCl were much less effective.…”

Section: Reviewsmentioning

confidence: 99%

“…(2)]. [19] The reaction was proven to be stereospecific by using cis-1,2-dideuterioethylene; no cis/trans isomerization accompanied the reversible addition. [20] A key observation from an elegant demonstration by Panunzi et al [21] was that diethylamine adds to a diastereomerically resolved platinum complex of the prochiral olefin 1-butene to give, after protonolysis, only (S)-N,N'-diethyl-sec-butylamine, the product of Markovnikov addition with anti stereochemistry [Eq.…”

Section: Nucleophilic Attack On Metal-coordinated Alkenes: Experimentsmentioning

confidence: 99%

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Electrophilic Activation of Alkenes by Platinum(II): So Much More Than a Slow Version of Palladium(II)

2007

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The electrophilic activation of alkenes by transition-metal catalysts is a fundamental step in a rapidly growing number of catalytic processes. Although palladium is the best known metal for this purpose, the special properties of its third-row cousin platinum (strong metal-ligand bonds and slow substitution kinetics) have enabled the development of transformations that are initiated by addition to the C=C bonds by protic carbon, nitrogen, oxygen, and phosphorus nucleophiles, as well as alkene or arene nucleophiles. Additionally, reactivity profiles, which are often unique to platinum, provide wholly new reaction products. This Review concerns platinum-catalyzed electrophilic alkene activation reactions, with a special emphasis on the mechanistic properties of known systems, on the differences between platinum and palladium catalysts, and on the prospects for the development of new systems.

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Section: Reviewsmentioning

confidence: 99%

Section: Nucleophilic Attack On Metal-coordinated Alkenes: Experimentsmentioning

confidence: 99%

Electrophilic Activation of Alkenes by Platinum(II): So Much More Than a Slow Version of Palladium(II)

2007

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“…This apparent rotation from addition -elimination, however, does not dissociate the alkene and may proceed as follows (in equation 7, Nu is a nucleophile, such as pyridine or phosphine). A π σ interconversion has been demonstrated for the pyridine nucleophile 76 …”

Section: Encyclopedia Of Inorganic and Bioinorganicmentioning

confidence: 96%

Stereochemical Nonrigidity of Organometallic Complexes

Faller

2005

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Compounds that undergo intramolecular rearrangements at rates that affect the NMR line shapes in generally accessible temperature ranges are described as stereochemically nonrigid. Analysis of 1D and 2D NMR spectra as a function of temperature often allow the rates, as well as the mechanisms of interconversion of conformers or isomers, to be determined. Examples were selected to illustrate the importance of stereochemical nonrigidity in reactivity and the potential for affecting stereochemistry in the products of reactions.

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Section: Characterizing Rotations and Barriersmentioning

confidence: 98%