A NMR Study of the Exchange Kinetics of the Nonamethylimidodiphosphoramide with its Complexes of Diamagnetic Cations

1978 ◽  
Vol 33 (6) ◽  
pp. 684-685 ◽  
Author(s):  
P. R. Rubini ◽  
L. Rodehüser ◽  
J.-J. Delpuech
Keyword(s):  
Nmr Spectroscopy ◽  
Ligand Exchange ◽  
H Nmr ◽  
Nmr Study ◽  
Exchange Kinetics ◽  
Monodentate Ligands ◽  
Kinetics Of

Abstract The ligand exchange on nonamethylimidodiphosphoramide (NIPA) complexes is found to be very slow comparatively to analogous monodentate ligands; the rates determined by 1H or 31P NMR spectroscopy are: k(25°C)=4.3 × 10-2 s-1; 31.6 s-1 • M-1; 3.7 × 104 S-1 • M-1 and 1.35 × 104 s-1 · M-1 for Mg2+, Ca2+, Sr2+ and Li+ cations respectively. For the Al3+, Ga3+, In3+ and Be2+ ions no exchange could be detected by 1H NMR spectroscopy up to 120 °C, indicating rates lower than about 10-3 s-1

scholarly journals Kinetics of ligand exchange between a uranium(IV) β-diketonate and free β-diketone

1977 ◽  
Vol 55 (20) ◽  
pp. 3559-3561 ◽  
Author(s):  
G. Folcher ◽  
N. Keller ◽  
C. Kiener ◽  
J. Paris
Keyword(s):  
Ligand Exchange ◽  
Free Ligand ◽  
Exchange Mechanism ◽  
First Order ◽  
H Nmr ◽  
Coordination Site ◽  
Exchange Kinetics ◽  
Kinetics Of

The intermolecular ligand exchange kinetics between a uranium(IV) β-diketonate and free β-diketone were studied by 1H nmr as a function of temperature and concentration. The reaction was found to be of first order in both chelate and free ligand. The results suggest that the exchange mechanism involves a ninth coordination site in the uranium(IV) chelate.

NMR study of ligand exchange in some metal dithiocarbamates

1980 ◽  
Vol 45 (6) ◽  
pp. 1785-1792 ◽  
Author(s):  
Ernest Beinrohr ◽  
Ján Garaj
Keyword(s):  
Thermal Stability ◽  
Nmr Spectroscopy ◽  
Ligand Exchange ◽  
Carbon Disulphide ◽  
H Nmr ◽  
Nmr Study ◽  
Metal Dithiocarbamates ◽  
Thermal Stability Of

The 1H-NMR spectroscopy was employed to study solutions of the dithiocarbamates of Cr(III), Fe(III), Co(III), Ni(II), Cu(II) and Zn(II) in carbon disulphide. It was confirmed that, in spite of the marked thermal stability of these complexes, ligand exchange occurs in solution, where the rate of exchange decreases in the order: Zn(II) Ni(II), Fe(III) Cu(II) Co(III), Cr(iii). The exchange practically does not occur in Co(III) and Cr(III) complexes.

scholarly journals Tautomerisation in 1-(4-Methylphenylazo)naphthalen-2-ol and 2-(4-Methylphenylazo)-4-methylphenol: A Crystallographic and 13C{1H}NMR Study

1999 ◽  
Vol 23 (3) ◽  
pp. 178-179
Author(s):  
Wendy I. Cross ◽  
Kevin R. Flower ◽  
Robin G. Pritchard
Keyword(s):  
Acetic Acid ◽  
Nmr Spectroscopy ◽  
Resonant Frequency ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Nmr Study ◽  
Acetic Acid Esters ◽  
Acid Esters ◽  
Equivalent Carbon

The acetic acid esters of 1-(4-methylphenylazo)naphthalen-2-ol 1 and 2-(4-methylphenylazo)-4-methylphenol 3 are prepared and characterised by single crystal X-ray diffraction studies and 13C{1H}NMR spectroscopy; the position of the C(2)13C resonance for the ester is used to predict the position of resonant frequency of the equivalent carbon in the parent alcohols and hence, calculate the position of the azo-hydrazone equilibrium in these compounds.

1H and 13C NMR Study of Proton Transfer in Azoles. Mechanism of Proton Transfer in Pyrazole in Solutions Containing bis-(Acetylacetonato) Nickel (II)

1976 ◽  
Vol 31 (7-8) ◽  
pp. 353-360 ◽  
Author(s):  
V. N. Babin ◽  
E. B. Zavelovidi ◽  
E. I. Fedin
Keyword(s):  
Proton Transfer ◽  
Ligand Exchange ◽  
Hyperfine Coupling ◽  
Outer Sphere ◽  
Coupling Constants ◽  
1H And 13C Nmr ◽  
Nmr Study ◽  
Nmr Techniques ◽  
Kinetics Of ◽  
C Nmr

Abstract Proton Transfer, Pyrazole, Outer-Sphere Coordination Proton transfer in pyrazole systems involving interaction with a paramagnetic transition metal complex has been studied with 1H and 13C NMR techniques. Kinetics of the ligand exchange in the pyrazole complex of bis-(acetylacetonato) nickel (II) has been investigated, and hyperfine coupling constants for the interaction of the nickel unpaired electron with the ligand nuclei in the complex have been determined. Catalytic admixtures of bis-(acetylacetonato) nickel (II) are shown to modify the mechanism of the proton transfer in pyrazole. The spectral data are discussed in terms of outer-sphere coordination and cooperative proton transfer effects.

scholarly journals Amino-functionalized (meth)acryl polymers by use of a solvent-polarity sensitive protecting group (Br-t-BOC)

2016 ◽  
Vol 12 ◽  
pp. 245-252
Author(s):  
Helmut Ritter ◽  
Monir Tabatabai ◽  
Markus Herrmann
Keyword(s):  
Free Radical ◽  
Nmr Spectroscopy ◽  
Free Amino ◽  
Solvent Polarity ◽  
Protecting Group ◽  
Amino Groups ◽  
Neighboring Group ◽  
H Nmr ◽  
Polarity Sensitive ◽  
Kinetics Of

We describe the synthesis of bromo-tert-butyloxycarbonyl (Br-t-BOC)-amino-protected monomers 2-((1-bromo-2-methylpropan-2-yl)oxycarbonylamino)ethyl (meth)acrylate 3a,b. For this purpose, 2-isocyanatoethyl (meth)acrylate 1a,b was reacted with 1-bromo-2-methylpropan-2-ol (2a). The free radical polymerization of (Br-t-BOC)-aminoethyl (meth)acrylates 3a,b yielded poly((Br-t-BOC)-aminoethyl (meth)acrylate) 6a,b bearing protected amino side groups. The subsequent solvolysis of the Br-t-BOC function led to the new polymers poly(2-aminoethyl (meth)acrylate) 8a,b with protonated free amino groups. The monomers and the resulting polymers were thoroughly characterized by 1H NMR, IR, GPC and DSC methods. The kinetics of the deprotection step was followed by 1H NMR spectroscopy. The solvent polarity and neighboring group effects on the kinetics of deprotection are discussed.

An NMR study of the complexes of Zn(II) and Cd(II) ions with tris(dimethylamino)phosphine sulphide: Ligand exchange kinetics

Polyhedron ◽  
1985 ◽  
Vol 4 (4) ◽  
pp. 643-647 ◽  
Author(s):  
K. Alouani ◽  
M.R. Khaddar ◽  
L. Rodehüser ◽  
P.R. Rubini ◽  
J.-J. Delpuech
Keyword(s):  
Ligand Exchange ◽  
Nmr Study ◽  
Exchange Kinetics
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