Reactions of transition metal-coordinated nitriles

Michelin, Rino A.; Mozzon, Mirto; Bertani, Roberta

doi:10.1016/0010-8545(94)01128-1

Cited by 450 publications

(259 citation statements)

References 204 publications

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“…The nitrile is proposed to undergo an intramolecular nucleophilic attack of the PMe 2 OH hydroxy placed in an armchair position Scheme 1. s-, p-and s,p-modes of coordination of nitriles. [17] Catalytic Hydration of Benzonitrile and Acetonitrile using Nickel(0) in cis-coordination, [24] leading to an oxo-bound, fivemembered ring imide complex which, after dihydrooxo-biaddition of a water molecule at the unsaturated C ¼ N bond of the imide ligand, produces the final oxobound hydroxy-carbamide complex. Metathesis of the oxo substituent for hydroxy at the PMe 2 armchair ligand would be likely to assist the decoordination of the amide and the regeneration of the catalyst, completing the catalytic cycle.…”

Section: Catalysis Of Nitrile Hydrationmentioning

confidence: 99%

“…[1] This is important considering that nitriles can interact with metal centers in two more ways, other than the terminal s-bonded, h 1 -NCR mode already mentioned, namely the p-bonded (side-on), or h 2 -NCR coordination, and the bridging s,p-bonded, mh 1 ,h 2 -NCR coordination, often found in clusters (Scheme 1). [17] A relevant series of tungsten-nitrile complexes, showing either s-or p-bonding, has been recently reported by Templetons group. [18] In this context, our group has also published a series of reports regarding the activation of aryl, heteroaryl and alkyl cyanides using the nickel(0) fragment [(dippe)Ni], that yield p-bonded h 2 -NCR complexes, such as [(dippe)Ni(h 2 -NCR)] (R ¼ phenyl or methyl; 1 and 2), respectively.…”

Section: Introductionmentioning

confidence: 96%

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Catalytic Hydration of Benzonitrile and Acetonitrile using Nickel(0)

2006

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Abstract:The homogeneous catalytic hydration of benzo-and acetonitrile under thermal conditions was achieved using nickel(0) compounds of the type [(dippe)Ni(h 2 -NCR)] with R ¼ phenyl or methyl (compounds 1 and 2, respectively), as the specific starting intermediates. Alternatively, the complexes may be prepared in situ by direct reaction of the precursor [(dippe)NiH] 2 (3) with the respective nitrile. Hydration appears to occur homogeneously, as tested by mercury drop experiments, producing benzamide and acetamide, respectively. Addition of Bu 4 NI did not lead to catalysis inhibition, suggesting the prevalence of Ni (0) intermediates during catalysis. Hydration using analogous complexes of 3, such as [(dtbpe)NiH] 2 (4) and [(dcype)NiH] 2 (5) was also addressed.

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Section: Catalysis Of Nitrile Hydrationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 96%

Catalytic Hydration of Benzonitrile and Acetonitrile using Nickel(0)

2006

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“…[ [17][18][19] Thus, the successful determination of the structure of complex 6 provides strong direct proof of the chemo-and regioselectivity of this zirconocene-mediated multicomponent synthesis of 5-azaindoles. The hydrolysis of 6 with water afforded the corresponding pyrroloA C H T U N G T R E N N U N G [3,2-c]pyridine derivative 4 b in a quantitative yield.…”

Section: Wwwchemeurjorgmentioning

confidence: 97%

One‐Pot Multicomponent Synthesis of Azaindoles and Pyrroles from One Molecule of a Silicon‐Tethered Diyne and Three or Two Molecules of Organonitriles Mediated by Zirconocene

Zhang

Sun

Zhang

et al. 2009

Chemistry A European J

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A zirconocene-mediated one-pot multicomponent synthesis process leading to the synthesis of pyrrolo[3,2-c]pyridine (5-azaindoles) and pyrrole derivatives has been developed starting from a silicon-tethered diyne and three or two different or identical organonitriles. Pyrrolo[3,2-c]pyridine and pyrrole derivatives with diverse structures and substitution patterns have been highly selectively prepared by this protocol. A wide variety of organonitriles and silicon-tethered diynes, either aliphatic or aromatic with both electron-withdrawing and -donating groups, have been used to afford 5-azaindoles and/or pyrroles in good-to-excellent isolated yields. A key intermediate formed in the Cp(2)Zr(II)-mediated reaction of one (PhC[triple bond]C)(2)SiMe(2), two molecules of iPrCN and one p-tolylCN was characterised by X-ray single-crystal structural analysis, which has allowed us to gain a good understanding of the reaction process.

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“…It has been known that the nitrile groups (-C≡N) in SAN are capable of coordinating to various transition metal ions. [25][26][27][28][29] When Cr(VI) is electrochemically reduced at the electrode surface, -C≡N can interact with Cr(III) in the ways of (I) terminal (end-on) σ-bonded or (II) π-bonded (side-on). 28,29 We suggest that ASV of Cr(VI) may well be facilitated at the Graphite-SAN composite electrode, due to a strong interaction between the reduced Cr(III) and -C≡N groups.…”

Section: Swasv Of Cr(vi) At a Graphite-san Composite Electrodementioning

confidence: 99%

Anodic Stripping Voltammetry for the Determination of Trace Cr(VI) with Graphite/Styrene-Acrylonitrile Copolymer Composite Electrodes

et al. 2017

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Although the addition of complexing agents is not necessary for ASV determination, so far only a few studies have been reported, probably due to the poor sensitivity and precision. Nevertheless, the oxidative stripping peak of Cr(VI) located in a more positive potential region that has much less interference by some heavy 2017 © The Japan Society for Analytical Chemistry † To whom correspondence should be addressed. A square-wave anodic stripping voltammetry (SWASV) for the determination of trace amounts of hexavalent chromium Cr(VI) at a graphite/styrene-acrylonitrile (Graphite-SAN) copolymer composite electrode is described. This method involves a preconcentration step whereby the trace Cr(VI) was cathodically reduced to Cr(III) on an electrode surface in an acetate buffer (pH 5), followed by an anodic stripping technique with a square-wave voltammetric mode. It has been shown that the analytical sensitivity is significantly improved at the Graphite-SAN copolymer composite electrode in comparison with the conventional glassy carbon electrode, due to the strong interaction between Cr(III) and the nitrile end group of the SAN copolymer. The SWASV response was characterized with respect to the pH, deposition potential, possible interferences, etc. Under the optimal conditions, the stripping peak height linearly increased with the concentration of Cr(VI) in a range from 0 to 150 ng mL -1 with a correlation coefficient of 0.997, and a detection limit of 4.2 ng mL -1was achieved based on signal-to-noise ratio of about 3. The Graphite-SAN composite electrode exhibited some interesting advantages, such as high mechanical rigid, easy surface renewable, higher sensitivity and better peak resolution in comparison with the results at conventional glassy carbon electrodes. They have been applied to the determination of Cr(VI) in real water samples with satisfactory recoveries.

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Reactions of transition metal-coordinated nitriles

Cited by 450 publications

References 204 publications

Catalytic Hydration of Benzonitrile and Acetonitrile using Nickel(0)

Catalytic Hydration of Benzonitrile and Acetonitrile using Nickel(0)

One‐Pot Multicomponent Synthesis of Azaindoles and Pyrroles from One Molecule of a Silicon‐Tethered Diyne and Three or Two Molecules of Organonitriles Mediated by Zirconocene

Anodic Stripping Voltammetry for the Determination of Trace Cr(VI) with Graphite/Styrene-Acrylonitrile Copolymer Composite Electrodes

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