Enantiomer-Specific Oxygen Exchange Reactions. 2. Acid-Catalyzed Water Exchange with 1-Phenyl-1-alkanols

1994 ◽  
Vol 116 (13) ◽  
pp. 5551-5559 ◽  
Author(s):  
Margaret V. Merritt ◽  
Dina B. Anderson ◽  
Kim A. Basu ◽  
I.-Wen Chang ◽  
Hee-Joo Cheon ◽  
...  
Keyword(s):  
Water Exchange ◽  
Oxygen Exchange ◽  
Exchange Reactions ◽  
Acid Catalyzed

Effect of electric fields on oxygen exchange reactions during sodium perchlorate thermolysis

2007 ◽  
Vol 413 (2) ◽  
pp. 81-83 ◽  
Author(s):  
S. M. Busurin ◽  
Yu. G. Morozov ◽  
M. V. Kuznetsov ◽  
M. L. Chernega
Keyword(s):  
Electric Fields ◽  
Sodium Perchlorate ◽  
Oxygen Exchange ◽  
Exchange Reactions

OXYGEN EXCHANGE REACTIONS OF BENZALDEHYDE AND SOME OTHER SUBSTANCES

1938 ◽  
Vol 2 (6) ◽  
pp. 569-573 ◽  
Author(s):  
MURRAY. SENKUS ◽  
WELDON G. BROWN
Keyword(s):  
Oxygen Exchange ◽  
Exchange Reactions ◽  
Other Substances

Interpretation of Activation Volumes for Water Exchange Reactions Revisited: AbInitioCalculations for Al3+, Ga3+, and In3+, and New Experimental Data

1998 ◽  
Vol 120 (26) ◽  
pp. 6569-6577 ◽  
Author(s):  
Th. Kowall ◽  
P. Caravan ◽  
H. Bourgeois ◽  
L. Helm ◽  
F. P. Rotzinger ◽  
...  
Keyword(s):  
Experimental Data ◽  
Water Exchange ◽  
Exchange Reactions

Heavy Oxygen Exchange Reactions of Proteins and Amino Acids

1939 ◽  
Vol 61 (4) ◽  
pp. 880-886 ◽  
Author(s):  
Whitney H. Mears ◽  
Harry. Sobotka
Keyword(s):  
Amino Acids ◽  
Oxygen Exchange ◽  
Exchange Reactions

Palladium(II) Catalyzed Exchange Reactions. XI. Vinyl Propionate Exchange with Acetic Acid Catalyzed by Palladium(II) Acetate

1975 ◽  
Vol 53 (15) ◽  
pp. 2223-2231 ◽  
Author(s):  
Raj N. Pandey ◽  
Patrick M. Henry
Keyword(s):  
Acetic Acid ◽  
Sodium Acetate ◽  
Exchange Reactions ◽  
Free System ◽  
Acetate Concentration ◽  
Rate Expression ◽  
Π Complex ◽  
Acid Catalyzed ◽  
Kinetics Of ◽  
Vinyl Propionate

The kinetics of the palladium(II) acetate catalyzed exchange of vinyl propionate with acetic acid solvent to give vinyl acetate has been studied in the sodium acetate concentration range from 0 to 1 M. The exchange rate first sharply increases as [NaOAc] increases, reaches a maximum at about 0.2 M and then gradually decreases as the sodium acetate concentration is in-creased to 1.0 M. Using previous results on the equilibrium between palladium(II) acetate and sodium acetate in acetic acid it can be shown that the rate expression for exchange is: rate = (ko + kt[Pd3(OAc)6] + kd[Na2Pd2(OAc)6]) [CH2=CHO2CC2H5] where ko = 2 × 10−4 s−1, kt = 0.045 M−1 s−1, and kd = 0.089 M−1 s−1. A monomeric palladium(II) species, Na2Pd(OAc)4, formed at high [NaOAc] is unreactive. Since the rate expression does not contain a term in [NaOAc], the sodium acetate serves only to convert one palladium(II) species to another. The lack of a [NaOAc] term in the rate expression for the Na2Pd2(OAc)6 catalyzed reaction is believed to result from cancellation of an inhibitory term for π-complex formation by a catalytic term in [NaOAc] in the rate determining conversion of π -complex to σ-complex (acetoxypalladation). Stereochemical studies indicate that acetoxypalladation is nonstereospecific. This result is expected since in the chloride free system acetate is both a ligand and a reactant. Thus it can attack from both inside and outside the coordination sphere of Pd(II).

Sign in / Sign up

Export Citation Format

Share Document