The hydrolysis of halogenopentamminechromium(III) complexes

1967 ◽  
Vol 20 (5) ◽  
pp. 893 ◽  
Author(s):  
SC Chan ◽  
KY Hui
Keyword(s):  
Bond Formation ◽  
The Other ◽  
Nucleophilic Substitutions ◽  
Hydroxide Ion ◽  
Solvent Water ◽  
Hydrolysis Of

The Croup Replacement Factors (G.R.F.) of halogens in nucleophilic substitutions of halogenopentamminechromium(III) complexes both by solvent water and by hydroxide ion have been compared with the corresponding data available for the analogous cobalt(III) cations. Although reactions in the latter system are typical SN2 processes with concurrent bond formation and fission, the mechanism of substitutions in halogenopentamminechromium(III) complexes depends on the nature of the halogen, being bimolecular for the fluoro and unimolecular for the other halogeno cations. The kinetic results are discussed partly along lines similar to those employed for the interpretation of organic nucleophilic substitutions.

The solvolytic aquation and base hydrolysis of halogenopentaammine-rhodium(III) complexes

1967 ◽  
Vol 20 (1) ◽  
pp. 61 ◽  
Author(s):  
SC Chan
Keyword(s):  
Activation Energy ◽  
Bond Formation ◽  
Base Hydrolysis ◽  
Hydroxide Ion ◽  
Sn2 Reactions ◽  
Solvent Water ◽  
Fluoro Complex ◽  
Entropy Factor ◽  
Opposing Effects ◽  
Hydrolysis Of

The rates and Arrhenius parameters for the replacement of halogens in halogenopentaamminerhodium(III) complexes both by solvent water and by hydroxide ion have been determined and their relative mobilities of halogens compared with the corresponding observations in organic compounds. These reactions are expected to follow the pattern of SNAr reactions, viz., F > Cl ≈ Br > I, and, except for the fluoro complex, this is now confirmed experimentally. The kinetic results are discussed and an attempt is made to interpret them in terms of the electronegativity of the halogens, which facilitates bond formation with the incoming nucleophile. Solvation factors are also important in the control of reactivities. For these reactions, the rate order depends on opposing effects of activation energy and entropy, with the former predominating, and in this way they are in complete contrast to SN2 reactions of octahedral cobalt(III) complexes where the entropy factor alone controls the rate.

Phosphato complexes of cobalt(III). IV. Hydrolysis in basic solution

1968 ◽  
Vol 21 (7) ◽  
pp. 1733 ◽  
Author(s):  
SF Lincoln ◽  
DR Stranks
Keyword(s):  
Isotope Effects ◽  
Base Hydrolysis ◽  
Basic Solution ◽  
Tracer Technique ◽  
Hydroxide Ion ◽  
Solvent Water ◽  
Coordination Spheres ◽  
Solvent Isotope ◽  
Hydrolysis Of ◽  
Solvent Isotope Effects

The rates of hydrolysis of phosphato complexes of cobalt(111) in sodium hydroxide concentrations ranging from 0.02M to 0.37M, and at several ionic strengths, have been measured with a tracer technique. Bidentate phosphato complexes exhibit the same rates of hydrolysis as the corresponding monodentate complexes, due to a rapid conversion of the bidentate into the monodentate form. The general rate law for base hydrolysis of all the phosphato complexes is: d[PO34]/dt = {kH2O + kOH[OH-]}[complex] At 60� and at unit ionic strength, the rate constants for the complexes cis-[Co(NH3)4OH.PO4]-, cis-[Co en2OH.PO4]-, and [Co(NH3)5PO4] respectively are: 103kH2O (min-l) 85.0, 2.0, <1; and 103kOH (1. mole-1 min-l) 42.7, 12.0, 69.5. Mechanistic conclusions have been based on the measured enthalpies and entropies of activation and deuterium solvent isotope effects. For all complexes, kH2O is identified with an aquation mechanism involving synchronous interchange of the phosphate and solvent water between the first and second coordination spheres of the complexes. In the case of the tetrammine and bis(ethylenediamine) complexes, kOH is identified with a process involving synchronous interchange of phosphate and hydroxide ion between the first and second coordination spheres of the complexes. In the case of the pentammine complex, an SN2CB mechanism is considered to be more probable. A comparison with the base hydrolysis of halogen complexes of cobalt(111) is presented.

Substitution reactions on arsenic(V). The formation and hydrolysis of pentaamminearsenatocobalt(III) in aqueous solution

1973 ◽  
Vol 26 (9) ◽  
pp. 1877 ◽  
Author(s):  
TA Beech ◽  
NC Lawrence ◽  
SF Lincoln
Keyword(s):  
Aqueous Solution ◽  
Ionic Strength ◽  
Bond Formation ◽  
The Other ◽  
Substitution Reactions ◽  
Rate Law ◽  
Hydrolysis Of ◽  
Hydrolysis Reactions

The formation of Co(NH3)5HAsO4+ and Co(NH3)5H2AsO42+ conforms to the rate law: ����������� rate = [Co(NH3)5H2O3+](k-1[HAsO42-]+k-2[H2AsO4-]) where k-1 = (11�1)x10-2 l. mol-1 s-1 and k-2 = (120�15)x10-4 l. mol-1 s-1 at 295 K and unit ionic strength. The hydrolysis of the arsenato complex conforms to the rate law: ������ rate = [total arsenato complex](Ka2k1+k2[H+]+k3[H+]2)(Ka2+[H+])-1 where k1 = (290�15)x10-7s-1, k2 = (408�20)x 10-6 s-1, k3 = (670�34)x10-3 l. mol-1 s-1, and pKa2 = 3.30�0.05 at 295 K and unit ionic strength. The formation and hydrolysis reactions proceed through bond formation and cleavage between oxygen and arsenic. The mechanisms of the reactions characterized by k1 and k-1 are considered to be associative substitutions on arsenic(v), but the mechanisms of the other reactions are less certain.

A FACILE SYNTHESIS AND REACTIONS OF AMINO SELENOLO[2,3-b]PYRIDINE CARBOXYLATE

2015 ◽  
Vol 12 (1) ◽  
pp. 3910-3918 ◽  
Author(s):  
Dr Remon M Zaki ◽  
Prof Adel M. Kamal El-Dean ◽  
Dr Nermin A Marzouk ◽  
Prof Jehan A Micky ◽  
Mrs Rasha H Ahmed
Keyword(s):  
Biological Activity ◽  
Carbonyl Compounds ◽  
Mass Spectra ◽  
The Other ◽  
Pyridine Derivatives ◽  
Facile Synthesis ◽  
High Biological Activity ◽  
Basic Hydrolysis ◽  
Pyridine Carboxylate ◽  
Hydrolysis Of

 Incorporating selenium metal bonded to the pyridine nucleus was achieved by the reaction of selenium metal with 2-chloropyridine carbonitrile 1 in the presence of sodium borohydride as reducing agent. The resulting non isolated selanyl sodium salt was subjected to react with various α-halogenated carbonyl compounds to afford the selenyl pyridine derivatives 3a-f  which compounds 3a-d underwent Thorpe-Ziegler cyclization to give 1-amino-2-substitutedselenolo[2,3-b]pyridine compounds 4a-d, while the other compounds 3e,f failed to be cyclized. Basic hydrolysis of amino selenolo[2,3-b]pyridine carboxylate 4a followed by decarboxylation furnished the corresponding amino selenolopyridine compound 6 which was used as a versatile precursor for synthesis of other heterocyclic compound 7-16. All the newly synthesized compounds were established by elemental and spectral analysis (IR, 1H NMR) in addition to mass spectra for some of them hoping these compounds afforded high biological activity.

Reactions of macroions with ester and carboxylic groups of polymers

1987 ◽  
Vol 52 (9) ◽  
pp. 2194-2203
Author(s):  
Miloslav Kučera ◽  
Dušan Kimmer ◽  
Karla Majerová ◽  
Josef Majer
Keyword(s):  
Maleic Anhydride ◽  
Acrylic Acid ◽  
Methyl Methacrylate ◽  
Bond Formation ◽  
Covalent Bond ◽  
The Other ◽  
Poly Methyl Methacrylate ◽  
Other Hand ◽  
Carboxylic Groups ◽  
Poly Acrylic Acid

In the reaction of dianions with poly(methyl methacrylate), only an insignificant amount of insoluble crosslinked product is obtained. If, however, the concentration of grafting dianions approaches that of ester groups, the amount of poly(methyl methacrylate) which may thus be crosslinked becomes quite significant. Dications, too, can bring about crosslinking of only an insignificant number of poly(methyl methacrylate) chains. Carboxylic groups in poly(acrylic acid) react with dianions and dications in an anhydrous medium similarly to ester groups. On the other hand, in the presence of a cocatalytic amount of water dications are more readily bound to carboxylic groups, forming a covalent bond. The relatively highest efficiency was observed in the bond formation between dication and the poly[styrene-alt-(maleic anhydride)], both in an anhydrous medium and in the presence of H2O.

Kinetic salt effects in the hydrolysis of ethyl malonate, methyl glutarate and ethyl adipate semiesters

1986 ◽  
Vol 51 (12) ◽  
pp. 2781-2785 ◽  
Author(s):  
M. Martín Herrera ◽  
J. J. Maraver Puig ◽  
F. Sánchez Burgos
Keyword(s):  
Salt Effect ◽  
Alkaline Media ◽  
Salt Effects ◽  
Coulombic Interaction ◽  
Hydroxide Ion ◽  
Ethyl Malonate ◽  
Hydrolysis Of

A study is made on the kinetic salt effect on the reaction of hydrolysis of several charged esters in alkaline media. The results are interpreted on the basis of the coulombic interaction, the salting in of hydroxide ion and a third component depending on size of the substrate.

THE ALDOBIOURONIC ACIDS OF HEMICELLULOSE B OF OAT HULLS

1956 ◽  
Vol 34 (3) ◽  
pp. 338-344 ◽  
Author(s):  
E. L. Falconer ◽  
G. A. Adams
Keyword(s):  
Glucuronic Acid ◽  
The Other ◽  
Partial Hydrolysis ◽  
Oat Hulls ◽  
Hydrolysis Of

Partial hydrolysis of hemicellulose B from oat hulls yielded two aldobiouronic acids, which were identified as 2-O-(4-O-methyl-α-D-glucopyruronosyl)-D-xylose and 2-O-(α-D-glucopyruronosyl)-D-xylose respectively. In addition, two aldotriouronic acids were isolated, one yielding on hydrolysis xylose and 4-O-methyl-glucuronic acid, and the other, xylose, galactose, and glucurone.

Heat capacity of activation for the hydrolysis of methanesulfonyl chloride and benzenesulfonyl chloride in light and heavy water

1969 ◽  
Vol 47 (22) ◽  
pp. 4199-4206 ◽  
Author(s):  
R. E. Robertson ◽  
B. Rossall ◽  
S. E. Sugamori ◽  
L. Treindl
Keyword(s):  
Heat Capacity ◽  
Free Energy ◽  
Temperature Dependence ◽  
Heavy Water ◽  
Bond Formation ◽  
Sulfonyl Chlorides ◽  
Benzenesulfonyl Chloride ◽  
Methanesulfonyl Chloride ◽  
Hydrolysis Of ◽  
Parameter Temperature Dependence

Rates of solvolysis of methanesulfonyl chloride and benzenesulfonyl chloride have been determined in H2O and D2O. The free energy, enthalpy, entropy, and heat capacity of activation were calculated. The exceptional accuracy of the data permitted an estimation of dΔCp≠/dT from a four parameter temperature dependence of the kinetic rates.From these data we conclude that both sulfonyl chlorides hydrolyse by the same mechanism (Sn2) The change in R from CH3 to C6H5 in RSO2Cl did not alter ΔCp≠ but ΔS≠ (20°) was changed from −8.32 to −13.25 cal deg−1 mole−1, respectively. The significance of this difference is attributed to the probability of bond formation rather than to differences in solvent reorganization.

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