The coordination chemistry of acrylonitrile

Bryan, Stephen J.; Huggett, Paul; Wade, Kenneth; Daniels, Jörg; Jennings, J. R.

doi:10.1016/s0010-8545(00)80520-2

Cited by 42 publications

(19 citation statements)

References 222 publications

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“…The crystal structure of 1a (Figure ) reveals somewhat interesting results that the bond distance of C⋮N (1.141(14) Å) of CH 2 CHCN is decreased upon coordination to Cp*Ir(η 3 -CH 2 CHCHPh) from that (1.163(1) Å) of free CH 2 CHCN, while the CC distance (1.353(2) Å) is increased from that (1.339(1) Å) of free CH 2 CHCN. These results are different from the data previously reported for Ni−NC−CHCH 2 and Cu−NC−CHCH 2 , where the CC distances are shorter than that of free CH 2 CHCN 1c. This lengthening of the CC distance of CH 2 CHCN in 1a led us to expect an increase in reactivity of the CC group.…”

Section: Resultscontrasting

confidence: 96%

“…Nitriles coordinated to transition metals show reactivity toward nucleophiles different from that of free nitriles probably because the coordination through the nitrogen atom increases the nucleophilicity of the carbon of the nitrile (N⋮ C −R) . Reactions of nitriles such as hydrolysis , and alcoholysis 3 are known to be catalyzed by metal complexes.…”

Section: Introductionmentioning

confidence: 99%

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Addition of OH^- and Alcohols or Amines to −C⋮N and −CHCH₂ Groups of CH₂CHCN Coordinated to Cp*Ir(η³-CH₂CHCHPh)

et al. 2000

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Hydroxide ion and alcohols or amines are added regioselectively to the -CtN and -CHd CH 2 groups of CH 2 dCHCN in [Cp*Ir(η 3 -CH 2 CHCHPh)(NCCHdCH 2 )] + (1a). The unsaturated amido complex Cp*Ir(η 3 -CH 2 CHCHPh)(NHCOCHdCH 2 ) (2a), alkoxo amido complexes Cp*Ir-and an amino iminoether complex [Cp*Ir(η 3 -CH 2 CHCHPh)(NHdC(OMe)CH 2 CH 2 NMe 2 )] + (8) have been prepared from the reactions of 1a with OH -, OH -/ROH (R ) Me, Et), OH -/HNR 2 (R 2 ) Me 2 , (Me)-(H)), and MeOH/NHMe 2 , respectively. Reactions of 2, 4, 6, and 8 with aqueous HCl yield Cp*IrCl(η 3 -CH 2 CHCHPh) and quantitative amounts of H 2 NCOCHdCH 2 , H 2 NCOCH 2 CH 2 -OR, H 2 NCOCH 2 CH 2 NR 2 , and MeOCOCH 2 CH 2 NMe 2 , respectively. Crystal structures of 1a and 4a have been determined by X-ray diffraction data analysis.

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Section: Resultscontrasting

confidence: 96%

Section: Introductionmentioning

confidence: 99%

Addition of OH^- and Alcohols or Amines to −C⋮N and −CHCH₂ Groups of CH₂CHCN Coordinated to Cp*Ir(η³-CH₂CHCHPh)

et al. 2000

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“…In 2:1 mixtures of 4 and acrylonitrile, a very slight displacement of the acrylonitrile chemical shifts was observed ( 13 C, 1 ppm downfield for the terminal carbon atom and the CN group, 0.5 ppm upfield for the internal carbon atom; 1 H, slight downfield shift (<0.05 ppm) for all protons). These are in agreement with a fast, incomplete and reversible N coordination of acrylonitrile to 4 . No effects were observed on morpholine resonances, even with excess 4 .…”

Section: Resultssupporting

confidence: 88%

Selective and Nonselective Aza-Michael Additions Catalyzed by a Chiral Zirconium Bis-Diketiminate Complex

et al. 2013

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Reaction of the chiral bis-diketiminate complex rac-or (R,R)-C 6 H 10 (nacnac Xyl ) 2 ZrCl 2 with AgOTf yielded the corresponding bis-triflate complex. The complex geometry changes from distorted octahedral in the dichloride complex to a pseudotetrahedral coordination involving π coordination of the diketiminate ligands. The bis-triflate complex is highly active for aza-Michael additions with turnover frequencies of 20000/h for the addition of morpholine to acrylonitrile and 1000/h for the addition of morpholine to methacrylonitrile. The enantioselectivities of the latter reaction in various solvents were low, never surpassing 19% ee. The reaction is first-order in olefin concentration and second order in amine concentration, which is explained by its participation as a base in the reaction mechanism. The presence of catalytic amounts of triethylamine slightly increases the observed rate constants and reduces the reaction order in amine to first order. Other activated alkenes such as methacrylonitrile, crotonitrile, methyl acrylate, and cyclohexenone can be employed, but no reactivity is observed toward styrene or vinyl ethers. Primary amines, secondary amines, and anilines can be employed as nucleophiles with activities correlating with their nucleophilicity, but the catalyst is unstable in the presence of alcohols.

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“…While acrylonitrile prefers to bond via the nitrogen atom to harder Lewis acids and displays a somewhat bridging coordination in the solid state structure of 3 (Figure ), complex 3 shows in solution the typical features of π-coordinated acrylonitrile: ,, The ν CN frequency of 2225 cm −1 is marginally lower than the one observed in the free olefin (2230 cm −1 ), while N-coordination should lead to significantly increased ν CN frequencies. As well, 13 C NMR resonances of the coordinated olefin (δ = 70.6 and 54.0 ppm) are shifted strongly upfield compared to free acrylonitrile (δ = 136.5 and 107.4 ppm), while no changes or slight upfield shifts would be expected for N-coordinated acrylonitrile.…”

Section: Resultsmentioning

confidence: 99%

π Back-Bonding in Dibenzyl-β-diketiminato Copper Olefin Complexes

Oguadinma

Schaper

2009

Organometallics

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N,N'-Dibenzyl-4-amino-2-iminopent-3-ene, nacnac Bn H, was obtained in a one-step synthesis starting from benzylamine and acetylacetone. Reaction of nacnac Bn H with CuOtBu in the presence of various Lewis bases gave the corresponding copper complexes (nacnac Bn )CuL (L: 2, styrene; 3, η 2acrylonitrile; 4, allyl phenyl ether; 5, stilbene; 7, xylylisonitrile; 8, triphenylphosphine). With diphenylacetylene (DPA) the dimeric complex {(nacnac Bn )Cu} 2 (μ-DPA), 6, was obtained. In the presence of excess DPA, 6 coordinates additional acetylene to form the monomeric complex (nacnac Bn )Cu(DPA), 6b. All complexes, with the exception of 4 and 6b, were characterized by X-ray diffraction studies. Structural and spectroscopic data indicate that π back-bonding in 2-8 is still weak when compared to other transition metals, but stronger than in most Cu(I) complexes. Olefin exchange experiments indicate preferred binding of electron-deficient olefins. Reaction of 3 with morpholine did not yield any hydroamination products, in agreement with significant π backbonding toward the olefin.

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The coordination chemistry of acrylonitrile

Cited by 42 publications

References 222 publications

Addition of OH^- and Alcohols or Amines to −C⋮N and −CHCH₂ Groups of CH₂CHCN Coordinated to Cp*Ir(η³-CH₂CHCHPh)

Addition of OH^- and Alcohols or Amines to −C⋮N and −CHCH₂ Groups of CH₂CHCN Coordinated to Cp*Ir(η³-CH₂CHCHPh)

Selective and Nonselective Aza-Michael Additions Catalyzed by a Chiral Zirconium Bis-Diketiminate Complex

π Back-Bonding in Dibenzyl-β-diketiminato Copper Olefin Complexes

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The coordination chemistry of acrylonitrile

Cited by 42 publications

References 222 publications

Addition of OH- and Alcohols or Amines to −C⋮N and −CHCH2 Groups of CH2CHCN Coordinated to Cp*Ir(η3-CH2CHCHPh)

Addition of OH- and Alcohols or Amines to −C⋮N and −CHCH2 Groups of CH2CHCN Coordinated to Cp*Ir(η3-CH2CHCHPh)

Selective and Nonselective Aza-Michael Additions Catalyzed by a Chiral Zirconium Bis-Diketiminate Complex

π Back-Bonding in Dibenzyl-β-diketiminato Copper Olefin Complexes

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Addition of OH^- and Alcohols or Amines to −C⋮N and −CHCH₂ Groups of CH₂CHCN Coordinated to Cp*Ir(η³-CH₂CHCHPh)

Addition of OH^- and Alcohols or Amines to −C⋮N and −CHCH₂ Groups of CH₂CHCN Coordinated to Cp*Ir(η³-CH₂CHCHPh)