The Mechanism of Toluene and Bibenzyl Formation from Benzylchromium Ion<sup>1</sup>

Kochi, Jay K.; Buchanan, D.H.

doi:10.1021/ja01082a028

Cited by 43 publications

(8 citation statements)

References 1 publication

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“…(H20)6CrLs+ + HsO+ ->-(H20)6Cr3+ + HL (5) Table IV contains a summary of the rate data for the aquation of the complexes studied. It is interesting to note that all of the complexes which have a hydroxyl function on the carbon atom bonded to the chromium aquate by two paths, of which one is zero order and the other first order in hydrogen ion concentration.…”

Section: Discussionmentioning

confidence: 99%

Oxidations of aqueous chromium(II). II. Chromium-carbon bond

Schmidt¹,

Swinehart²,

Taube³

1971

J. Am. Chem. Soc.

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An investigation of the formation and kinetic stability of complexes containing a chromium-carbon bond in an aqueous medium is described. Pentaaquochromium(III) ions carbon bonded to small acyclic anions such as are derived from isopropyl alcohol and diethyl ether are formed by the reduction of organic radicals with Cr(II). The organic radicals are produced by hydrogen abstraction with OH radicals. Aquation rates of the Cr(III) complexes when the organic ligands contain hydroxyl groups (alcohols) are described by the differential rate lawd In [(H20)5CrL2+]/df = k_ -k2[H+], The rate laws for complexes having organic ligands which do not have a hydroxyl group (e.g., methyl or the radical derived from diethyl ether) do not show the term independent of hydrogen ion. A mechanism is proposed in which the activated complex contains a solvent molecule in a position so as to take advantage of hydrogen bonding with the organic ligand.

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Section: Discussionmentioning

confidence: 99%

Oxidations of aqueous chromium(II). II. Chromium-carbon bond

Schmidt¹,

Swinehart²,

Taube³

1971

J. Am. Chem. Soc.

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“…trtm-Stilbene oxide was prepared by the reaction of peroxyacetic acid with (twu-stilbene.27 erytAo-Hydrobenzoin monoethyl ether was prepared by refluxing tra/H-stilbene oxide in ethanol with a tenfold excess of sodium ethoxide. Two crystallizations of the product from pentane at Dry Ice temperature gave white crystals: mp 51-52°( lit.28 45-50°); nmr (CC14) 7.05 (m, 10, Ph), AB pattern centered about 4.42 (J = 6 Hz, = 29 Hz, 2, PhCAf); 3.25 (m, 2, OCtf2CH3);…”

Section: Methodsmentioning

confidence: 99%

Reductive coupling of benzaldehyde by chromium(II) salts

Davis¹,

Bigelow²

1970

J. Am. Chem. Soc.

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Benzaldehyde is reduced by Cr(II) salts in aqueous acidic ethanol to hydrobenzoin and the ethyl ethers of hydrobenzoin. A kinetic study of the reaction indicates a multipath reaction mechanism, with a rate law of the form, ¿obsd[A mechanism is proposed which involves initial ligand-transfer reduction of a halohydrin or a protonated hydrate (or hemiacetal) of benzaldehyde. Similar reduction of "dimeric" forms of benzaldehyde addition compounds are suggested to account for two terms in the rate law. An organochromium species is postulated as an intermediate in the formation of the coupled products.

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“…Most of the isolated Cr III –alkyl complexes slowly decompose in solution at room temperature forming Cr 2+ and free R radicals that in turn produce the corresponding alkane RH and the coupling product RR 1a. c–e, h…”

Section: Organic Products Of the Reactions Of V2+ And Cr2+ With Chbr3mentioning

confidence: 99%

Metal Ions Do Not Play a Direct Role in the Formation of Carbon–Carbon Triple Bonds during Reduction of Trihaloalkyls by Cr^II or V^II

Levy

Bino

2012

Chemistry A European J

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Carbyne radicals: Reactions of trihaloalkyl compounds with Cr(2+) or V(2+) in aqueous solutions yield alkynes and other products. Stepwise halogen abstractions from the trihaloalkyls form alkyl carbyne triradicals in solution. These radicals undergo coupling reactions, producing triply bonded alkyne molecules (see scheme). This process is not metal-assisted and does not occur in the coordination sphere of the metal ions.

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The Mechanism of Toluene and Bibenzyl Formation from Benzylchromium Ion¹

Cited by 43 publications

References 1 publication

Oxidations of aqueous chromium(II). II. Chromium-carbon bond

Oxidations of aqueous chromium(II). II. Chromium-carbon bond

Reductive coupling of benzaldehyde by chromium(II) salts

Metal Ions Do Not Play a Direct Role in the Formation of Carbon–Carbon Triple Bonds during Reduction of Trihaloalkyls by Cr^II or V^II

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The Mechanism of Toluene and Bibenzyl Formation from Benzylchromium Ion1

Cited by 43 publications

References 1 publication

Oxidations of aqueous chromium(II). II. Chromium-carbon bond

Oxidations of aqueous chromium(II). II. Chromium-carbon bond

Reductive coupling of benzaldehyde by chromium(II) salts

Metal Ions Do Not Play a Direct Role in the Formation of Carbon–Carbon Triple Bonds during Reduction of Trihaloalkyls by CrII or VII

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The Mechanism of Toluene and Bibenzyl Formation from Benzylchromium Ion¹

Metal Ions Do Not Play a Direct Role in the Formation of Carbon–Carbon Triple Bonds during Reduction of Trihaloalkyls by Cr^II or V^II