Heterolytic Cleavage of the C−C Bond of Acetonitrile with Simple Monomeric CuII Complexes: Melding Old Copper Chemistry with New Reactivity

Marlin, Dana S.; Olmstead, Marilyn M.; Mascharak, Pradip K.

doi:10.1002/1521-3773(20011217)40:24<4752::aid-anie4752>3.0.co;2-l

Cited by 81 publications

(46 citation statements)

References 12 publications

(17 reference statements)

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“…This should result in electron flow from the π bond to the M II atom and increase the “leaving ability” of cyanide and the electrophilicity of the alkyl or aryl carbon atom, resulting in cleavage by adventitious water to form alcohol and a receptor–substrate complex of [ML(CN)] 3+ . This unique mechanism of CC bond cleavage by an S N 2‐type process is different from those reported previously,3, 7 and, to our knowledge, has not been reported before.…”

Section: Resultscontrasting

confidence: 94%

“…On the S N 1 pathway, [Cu 2 L] 4+ first cleaves the CC bond of CH 3 CN to give CH 3 + and CN − , followed by transformation of CH 3 + into CH 3 OH in the presence of water (Equation (3) in Scheme ). Indeed, cleavage of CH 3 CN into CH 3 + and CN − by a mononuclear Cu II complex has been previously reported 7. On the other hand, simultaneous cleavage of the CC bond of CH 3 CN by [Cu 2 L] 4+ and water via an S N 2 pathway can also afford [Cu 2 L(CN)] 3+ and CH 3 OH (Eq.…”

Section: Introductionmentioning

confidence: 89%

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Mechanistic Studies of CC Bond Cleavage of Nitriles by Dinuclear Metal Cryptates

Yang

Zhuang

et al. 2009

Chemistry A European J

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We previously reported that dinuclear copper(II) cryptate [Cu(2)L](4+) cleaves the C-C bond of acetonitrile at room temperature to produce a cyano-bridged dinuclear cryptate and methanol, whereby the reaction mechanism has not yet become clear. We have now systemically investigated this reaction, and four cryptates, [Cu(2)L](ClO(4))(4) (1), [Zn(2)L](ClO(4))(4) (2), [Cu(2)L(H(2)O)(2)](CF(3)SO(3))(4) (5), and [Cu(2)L(OH)(OH(2))](ClO(4))(3) (6) are reported here. Cryptates 1 and 2 can cleave the C--C bonds of acetonitrile, propionitrile, and benzonitrile at room temperature under open atmospheric conditions to give cyano-bridged cryptates [Cu(2)L(CN)](ClO(4))(3) (3) and [Zn(2)L(CN)](ClO(4))(3) (4), respectively, and the corresponding alcohol. In contrast, 5 and 6 do not show any C-C bond activation of nitriles, as the interior axial positions of Cu(II) in 5 and 6 are occupied by water/OH(-). The C-C bond cleavage of (S)-(+)-2-methylbutyronitrile by 2 produced (R)-(-)-2-butanol only; that is, the cleavage reaction proceeds through an S(N)2 pathway (Walden inversion).

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Section: Resultscontrasting

confidence: 94%

Section: Introductionmentioning

confidence: 89%

Mechanistic Studies of CC Bond Cleavage of Nitriles by Dinuclear Metal Cryptates

Yang

Zhuang

et al. 2009

Chemistry A European J

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“…The geometry nicely agrees with the X-ray structure [29]. In agreement with this theoretical arguments, the majority of X-ray structure determinations on tris(ethylenediamine) metal complexes revealed Δλλλ or Λδδδ configuration and none for Cu(II) mixed ring conformations, according to the Cambridge Structural Database (CSD).…”

Section: +supporting

confidence: 79%

DFT study of the Jahn–Teller effect in Cu(II) chelate complexes

Gruden¹,

Zlatar²,

Schläpfer³

et al. 2010

Journal of Molecular Structure: THEOCHEM

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“…The results also complement reports of scission of the C-C bond in CH 3 CN by Cu(II) complexes. [13] While this work was nearing completion, a report of the synthesis and X-ray structure of (Et 4 N) 3 appeared. [14] …”

Section: Introductionmentioning

confidence: 99%

Reactivity of (Dicarboxamide)M^II–OH (M = Cu, Ni) Complexes – Reaction with Acetonitrile to Yield M^II–Cyanomethides

et al. 2013

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The complexes (Bu4N)(LMeM(II)-OH) (LMe = 2,6-dimethylphenyl-substituted pyridine(dicarboxamide); M = Cu or Ni) react with CH3CN to yield (Bu4N)(LMeM-CH2CN), novel cyanomethide complexes that were fully characterized, including by X-ray crystallography. These conversions contrast with the usual reactions of metal-hydroxide complexes with nitriles, which typically involve attack at the nitrile carbon and formation of amides or carboxylic acids. Kinetic studies (M = Cu) revealed a first-order dependence on the complex and a kinetic isotope effect (k(CH3CN)/k(CD3CN) of 4. Various mechanisms involving either intra- or intermolecular deprotonation steps are proposed. In addition, (Bu4N)(LMeCu-OH) was oxidized by Fc+PF6− to a proposed Cu(III) complex LMeCuOH at low temperature, and comparisons of its stability and reactivity with dihydroanthracene were drawn to its previously described congener having isopropyl substituents on the phenyl rings of the supporting ligand. The cyanomethide complex (Bu4N)(LMeCu(CH2CN)) also was reversibly oxidized both electrochemically (E1/2 = −0.345 V vs. Fc/Fc+) and chemically (Fc+PF6−, −25 °C). The product was formulated as LMeCu(III)(CH2CN), a novel Cu(III)-alkyl complex relevant to such species proposed during copper-catalyzed organic reactions.

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Heterolytic Cleavage of the C−C Bond of Acetonitrile with Simple Monomeric CuII Complexes: Melding Old Copper Chemistry with New Reactivity

Cited by 81 publications

References 12 publications

Mechanistic Studies of CC Bond Cleavage of Nitriles by Dinuclear Metal Cryptates

Mechanistic Studies of CC Bond Cleavage of Nitriles by Dinuclear Metal Cryptates

DFT study of the Jahn–Teller effect in Cu(II) chelate complexes

Reactivity of (Dicarboxamide)M^II–OH (M = Cu, Ni) Complexes – Reaction with Acetonitrile to Yield M^II–Cyanomethides

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Heterolytic Cleavage of the C−C Bond of Acetonitrile with Simple Monomeric CuII Complexes: Melding Old Copper Chemistry with New Reactivity

Cited by 81 publications

References 12 publications

Mechanistic Studies of CC Bond Cleavage of Nitriles by Dinuclear Metal Cryptates

Mechanistic Studies of CC Bond Cleavage of Nitriles by Dinuclear Metal Cryptates

DFT study of the Jahn–Teller effect in Cu(II) chelate complexes

Reactivity of (Dicarboxamide)MII–OH (M = Cu, Ni) Complexes – Reaction with Acetonitrile to Yield MII–Cyanomethides

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Reactivity of (Dicarboxamide)M^II–OH (M = Cu, Ni) Complexes – Reaction with Acetonitrile to Yield M^II–Cyanomethides