Fluorinated alkoxides. Part XI. Studies on highly fluorinated amino-alcohols and their metal derivatives

1977 ◽  
Vol 55 (13) ◽  
pp. 2465-2472 ◽  
Author(s):  
In-Soon Chang ◽  
Christopher J. Willis
Keyword(s):  
Donor Site ◽  
Amino Alcohols ◽  
Formation Constants ◽  
Intramolecular Proton Transfer ◽  
Nitrogen Donor ◽  
Metal Derivatives ◽  
Fluorinated Alcohol ◽  
Fluorinated Alkoxides ◽  
Trifluoromethyl Groups ◽  
Steric Influence

We describe the synthesis of a number of difunctional molecules in which the fluorinated tertiary alcohol grouping, -C(CF3)20H, is combined with a nitrogen donor site such as an amino-group or a pyridine ring. In all cases, zwitterionic behaviour in solution is found resulting from intramolecular proton transfer from the acidic fluorinated alcohol to the nitrogen, and this sometimes persists in the solid state, e.g. NH2CH2CH2C(CF3)20H exists as the dipolar ion +NH3CH2CH2C(CF3),0-. Measurements of pK values suggest that the behaviour of the fluorinated amino-alcohols may be compared with that of the amino-acids, subject to changes to be expected from the lower acidity of the -C(CF3)20H group. Metal complexes of the fluorinated amino-alcohols form readily; specifically, neutral complexes of Co2+, Ni2+, and Cu2+ of formula M(L),, where L is an ionized amino-alcohol chelating through the ionized hydroxy group and the nitrogen atom. Measurements of formation constants show that the six-membered chelate rings are the most stable, while a comparison of the stabilities of fluorinated amino-alkoxy complexes with those of analogous aminoacids shows that the former are less stable: this is attributed to the steric influence of the trifluoromethyl groups.

Fluorinated alkoxides. Part XIII. The reduction of β-imino-alkoxy complexes to give stable, polydentate, amino-alcohols; their coordination to Co2+, Ni2+, and Cu2+

1978 ◽  
Vol 56 (23) ◽  
pp. 2966-2969 ◽  
Author(s):  
John W. L. Martin ◽  
C. J. Willis
Keyword(s):  
Metal Atom ◽  
Amino Alcohols ◽  
Fluorinated Alcohol ◽  
Fluorinated Alkoxides

The amino-alcohols HOC(CF3)2CH2CH(CH3)NH(CH2)3NHCH(CH3)CH2C(CF3)2OH and HOC(CF3)2CH2CH(CH3)NH(CH2)3NH(CH2)3NHCH(CH3)CH2C(CF3)2OH have been prepared by reduction of the corresponding imino-alcohols coordinated to, e.g., Cu2+, by use of LiAlH4. The products are capable of acting as polydentate, dinegative, ligands (following ionization of the fluorinated alcohol groups) and the second compound gives stable, neutral, complexes of Co2+, Ni2+, and Cu2+ in which the metal atom is five-coordinate.

Fluorinated alkoxides. Part XII. Studies on potentially tridentate fluorinated diols; zwitterionic and five-coordinate complexes of Ni2+ and Cu2+

1978 ◽  
Vol 56 (17) ◽  
pp. 2369-2373 ◽  
Author(s):  
Stephen J. Loeb ◽  
John W. L. Martin ◽  
Christopher J. Willis
Keyword(s):  
Steric Effects ◽  
Bidentate Ligands ◽  
Tridentate Ligands ◽  
The Third ◽  
Complexing Ability ◽  
Fluorinated Alcohol ◽  
Fluorinated Alkoxides

The complexing ability towards Ni2+ and Cu2+ of the potentially tridentate ligands HOC(CF3)2CH2C(O)CH2C(CF3)2OH, HOC(CF3)2CH2CH(OH)CH2C(CF3)2OH, and HOC(CF3)2CH2CH2N:C(CH3)CH2C(CF3)2OH has been studied. The first two act as bidentate ligands, uninegative or dinegative according to the extent of ionization of the fluorinated alcohol groups; when both were ionized, the complexes had a zwitterionic structure. The third ligand was exclusively tridentate in its complexes; this difference is ascribed to its greater flexibility. Both four- and five-coordinate complexes of nickel were observed, the latter being produced either by choice of co-ligands or by solvation, but no six-coordinate complex was formed in this series. Limitations on coordination for the metal are ascribed to steric effects.

The Affinity of Indium(III) for Nitrogen-donor Ligands in Aqueous Solution. A Study of the Complexing of Indium(III) with Polyamines by Differential Pulse Voltammetry, Density Functional Theory, and Crystallography

2007 ◽  
Vol 62 (3) ◽  
pp. 386-396 ◽  
Author(s):  
James M Harrington ◽  
Karen A. Oscarson ◽  
S. Bart Jones ◽  
Joseph H. Reibenspies ◽  
Libero J. Bartolotti ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Differential Pulse Voltammetry ◽  
Density Functional ◽  
Differential Pulse ◽  
Formation Constants ◽  
Donor Ligands ◽  
Nitrogen Donor Ligands ◽  
Diglycolic Acid ◽  
Nitrogen Donor ◽  
Pulse Voltammetry

The affinity of In(III) for N-donor ligands was investigated by differential pulse voltammetry, DFT calculations, and crystallography. The structure of [In(tpen)(CH3COO)](ClO4)2 ・ 0.5H2O (1) is reported (tpen = N,N,N´ ,N´-tetrakis(2-pyridylmethyl)ethylenediamine): Monoclinic, P21/n, a = 8.687(4), b = 7.767(8), c = 20.432(10) Å , β = 93.372(8)°, Z = 4, R = 0.0518. The In(III) center is 7-coordinate, with six In-N bonds to the tpen ligand in the range 2.306 - 2.410 Å, and a unidentate acetate group with In-O = 2.247 Å. The formation constants of In3+ in 0.1 M NaNO3+ at 25 °C are (M = In(III), L = ligand, H = proton): L = triethylenetetramine, logβ (MLH2) = 25.3±}0.3, logK1 = 14.43±}0.09, and logβ (ML(OH)2) = 27.7±}0.1; tetraethylenepentamine, logβ (MLH) = 20.8±}0.2, and ML (logβ (ML) = 20.1±}0.3); diglycolic acid, (logβ (MLH) = 8.06±}0.06), logK1 = 6.02±} 0.06, logβ2 = 9.40±}0.08; tpen, logK1 = 17.71±}0.07; N,N´-bis(2-pyridylmethyl)ethylenediamine, logK1 = 14.69±}0.05; 1,10-phenanthroline, logK1 = 6.81±}0.07, logK2 = 6.44±}0.07, logK3 = 6.20±}0.08. Correlations are shown between the determined formation constants for the polyamines and logK1(NH3) values for a wide variety of metal ions. For M(II) ions, the log K1(NH3) values are experimental data, but for M(III) ions the data are predicted by an empirical dual-basicity equation, including logK1(NH3) = 4.0 for In(III). DFT calculations are used to obtain ΔE for the reaction [M(H2O)6]n+ + NH3 ⇆[M(H2O)5NH3]n+ + H2O for M(II) through M(IV) ions in water, represented as a structureless medium with the dielectric constant of water. Correlations are found that support the predicted value of logK1(NH3) for In(III) of 4.0. The nature of the intercepts on such correlations are discussed.

ChemInform Abstract: New Unsymmetrical Tetradentate Macrocycles with sp3 and sp2 Nitrogen Donor Site-Synthesis and Ru(II) Complexation.

ChemInform ◽  
2010 ◽  
Vol 23 (17) ◽  
pp. no-no
Author(s):  
G. TARRAGO ◽  
S. EL KADIRI ◽  
C. MARZIN ◽  
C. COQUELET
Keyword(s):  
Donor Site ◽  
Nitrogen Donor

Tetrabenzoporphyrins: Metal Incorporation and Exchange Kinetics, Ligational Equilibria and Pulse Radiolysis Studies

1997 ◽  
Vol 01 (01) ◽  
pp. 45-54 ◽  
Author(s):  
S. CROMER ◽  
P. HAMBRIGHT ◽  
J. GRODKOWSKI ◽  
P. NETA
Keyword(s):  
Kinetic Studies ◽  
Radical Cations ◽  
Formation Constants ◽  
Solution Chemistry ◽  
Exchange Reactions ◽  
Cadmium Ion ◽  
Metal Derivatives ◽  
Exchange Kinetics ◽  
Ion Incorporation ◽  
Metal Incorporation

The solution chemistry of tetrabenzoporphyrin ( TBP ) and several of its metal derivatives were compared with that of the corresponding octaethylporphyrins. Kinetic studies were done on zinc and cadmium ion incorporation and the exchange reactions of cadmium porphyrins with zinc. Formation constants of Cd (II), Cu (II), VO (IV), Ni (II), Zn (II) and Mg (II) porphyrins with pyridine were determined for both compounds. The spectra of the radical cations of Ni (II), Mg (II) and H 2- TBP were obtained, as well as that of the radical anion of Mg (II)- TBP . Aside from the new Ni (I)- TBP , no long-lived intermediates, as noted with other porphyrins, were observed upon reduction of the tetrabenzoporphyrins. The low basicity and rigidity of the tetrabenzoporphyrin nucleus may explain many of its relative reactivity properties.

Formation Constants of some Metal Derivatives: S-Alkyl Carboxylic Acids

1956 ◽  
Vol 60 (10) ◽  
pp. 1427-1429 ◽  
Author(s):  
Roger J. Irving ◽  
W. Conard Fernelius
Keyword(s):  
Carboxylic Acids ◽  
Formation Constants ◽  
Metal Derivatives
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