A Secondary Kinetic Isotope Effect in a Substitution Reaction of a Square-Planar Complex

Falk, Charles D.; Halpern, Jack

doi:10.1021/ja01091a037

Cited by 6 publications

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“…with pyridine, Ah/Ad = 1.44, and has been taken as evidence for the formation of five-coordinate intermediate in a Sn2 type of mechanism. 18 The present observed isotopic effect, Ah/Ad = 1.34, is inconsistent with this scheme (see below).…”

Section: Resultscontrasting

confidence: 54%

Kinetics and mechanism of the reaction of methyl acrylate with trans-bis(triethylphosphine)hydridoplatinum(II) nitrate

Clark¹,

Wong²

1974

J. Am. Chem. Soc.

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Section: Resultscontrasting

confidence: 54%

Kinetics and mechanism of the reaction of methyl acrylate with trans-bis(triethylphosphine)hydridoplatinum(II) nitrate

Clark¹,

Wong²

1974

J. Am. Chem. Soc.

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“…(2) D20 decreased the rate of methane formation but did not influence the formation of ethylene and ethane proportionally. If reduction of methyl isocyanide involved successive attacks on the bound radical by hydrogen, the rate of methane formation could be considerably slower in D20 (Falk & Halpern, 1965), but the interaction of two Cl radicals would be unaffected and therefore ethylene and ethane could be produced at a relatively faster rate in D20 than in H120.…”

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confidence: 99%

Reduction of Cyanide and Isocyanide by Nitrogenase of Azotobacter chroococcum

Kelly¹,

Postgate²,

Richards³

1967

Biochemical Journal

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Burns & Bulen (1965) showed that cell-free extracts of Azotobacter vinelandii contained an ATP-activated system capable of fixing nitrogen. When provided with sodium dithionite and an ATPgenerating system, their preparations evolved less hydrogen under nitrogen than under argon, the difference being accountable as nitrogen reduced to ammonia. Hardy & Knight (1966b) showed that dithionitedependent adenosine-triphosphatase activity was associated with nitrogen fixation. More recently preparations from A. vinetandii and Cloetridium pa8teurianum have been found to reduce a variety of additional substrate including acetylene (Dilworth, 1966), nitrous oxide, N3-and CN-ions (Hardy & Knight,1966a). We now report that nitrogen-fixing extracts of Azotobacter chroococcum reduce not only CN-ions but also methyl isocyanide, and indicate the relevance of these reactions to the mechanism of nitrogen fixation. Methods and Materials. Active cell-free extracts from A. chroococcum (N.C.I.B. 8003) grown on the nitrogen-free sucrose medium of Burk, Newton, Wilson & Harris (1953) were obtained by disruption at pH7-4 with ultrasound by using a Dawe Soniprobe. Whole cells and debris were removed by centrifuging at 18000g for 30min. and the supernatant was heated for 7min. at 600 under an atmo

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The Intimate Mechanism of Replacements in d ⁸ Square‐Planar Complexes

Cattalini

1970

Progress in Inorganic Chemistry

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A Secondary Kinetic Isotope Effect in a Substitution Reaction of a Square-Planar Complex

Cited by 6 publications

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Kinetics and mechanism of the reaction of methyl acrylate with trans-bis(triethylphosphine)hydridoplatinum(II) nitrate

Kinetics and mechanism of the reaction of methyl acrylate with trans-bis(triethylphosphine)hydridoplatinum(II) nitrate

Reduction of Cyanide and Isocyanide by Nitrogenase of Azotobacter chroococcum

The Intimate Mechanism of Replacements in d ⁸ Square‐Planar Complexes

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A Secondary Kinetic Isotope Effect in a Substitution Reaction of a Square-Planar Complex

Cited by 6 publications

References 0 publications

Kinetics and mechanism of the reaction of methyl acrylate with trans-bis(triethylphosphine)hydridoplatinum(II) nitrate

Kinetics and mechanism of the reaction of methyl acrylate with trans-bis(triethylphosphine)hydridoplatinum(II) nitrate

Reduction of Cyanide and Isocyanide by Nitrogenase of Azotobacter chroococcum

The Intimate Mechanism of Replacements in d 8 Square‐Planar Complexes

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The Intimate Mechanism of Replacements in d ⁸ Square‐Planar Complexes