Organonitrile complexes of transition metals

Storhoff, Bruce N.; Lewis, Huntley C.

doi:10.1016/s0010-8545(00)80329-x

Cited by 411 publications

(196 citation statements)

References 143 publications

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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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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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“…The mode of acetonitrile (or any alkyl cyanide) bonding to transition metals in mononuclear or polynuclear complexes, with one exception, simply comprises a a bond between the nitrile nitrogen atom and a single metal atom (9). Although side, v bonding of nitriles has been been claimed, none is structurally establishedfor acetonitrile or a simple alkyl isoëyanide (9).…”

Section: Unauthenticatedmentioning

confidence: 99%

“…Although side, v bonding of nitriles has been been claimed, none is structurally establishedfor acetonitrile or a simple alkyl isoëyanide (9). Unlike carbon monoxide, acetonitrile is not known to form two electron bridge bonds between two or three metal atoms.…”

Section: Unauthenticatedmentioning

confidence: 99%

Coordination chemistry of metal surfaces and metal complexes

Muetterties

1980

Pure and Applied Chemistry

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-The coordination chenistry of two isomeric molecules, acetonitrile and nethyl isocyanide, has been characterized for (A) single crystal nickel surfaces as a function of crystallography and surface composition, (B) nickel catalyst surfaces,and (C) molecular mononuclear and polynuclear metal complexes. Conditions have been established for the catalytic isomerization of methyl isocyanide to acetonitrile within these nickel surface and molecular complex regimes. A comparison is made of the acetonitrile and methyl isocyanide chemistry between the surface and molecular complex areas.

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“…Two types of CCN bond activation are available: the oxidative addition of CCN bonds to lowvalent transition-metal complexes, 6 and the formation of silyl isonitrile complexes through cleavage of CCN bonds. 7 The high affinity of a cyano group for transition metals, which allows its coordination to a metal center in either an η 1 -or η 2 -fashion, 8 acts as a kinetic driving force, whereas the formation of strong metalCN bonds 9 acts as a thermodynamic driving force of the elementary reaction step. Both reactions have already been applied to catalytic transformations of nitriles through the cleavage of CCN bonds.…”

Section: Introductionmentioning

confidence: 99%

Nickel/Lewis Acid-Catalyzed Carbocyanation of Unsaturated Compounds

Nakao

2012

Bulletin of the Chemical Society of Japan

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Addition reactions of the organic and cyano groups of nitriles through cleavage of the CCN bonds, namely carbocyanation, have been developed using nickel/Lewis acid (LA) cooperative catalysis. Originally, the reaction was performed with a nickel catalyst alone and was limited to the use of aryl and allyl cyanides as the nitrile substrates. By employing LA cocatalysts, the rate of the arylcyanation was accelerated significantly and the scope of nitriles used in the reaction across alkynes was expanded to include alkenyl, alkynyl, and alkyl cyanides. The high chemo-, regio-, and stereoselectivities of the alkynecarbocyanation reactions were highlighted by the syntheses of biologically active compounds including the synthetic precursor of P-3622 and plaunotol, which possess defined tri-or tetrasubstituted ethene structures. Intramolecular arylcyanation of alkenes was also achieved by cooperative catalysis. Mechanistic studies on this particular transformation allowed us to identify several reaction intermediates, which revealed the modes of the cooperative catalysis derived from nickel-and aluminum-based LA. Intramolecular arylcyanation was achieved in an enantioselective manner using optically active bidentate phosphorus ligands, affording a protocol to introduce both a quaternary stereocenter and a cyano functionality without by-product generation.

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Organonitrile complexes of transition metals

Cited by 411 publications

References 143 publications

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

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

Coordination chemistry of metal surfaces and metal complexes

Nickel/Lewis Acid-Catalyzed Carbocyanation of Unsaturated Compounds

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