A nuclear magnetic resonance study of ligand exchange on dioxopentakis(trimethyl phosphate)uranium(VI) ion and its triethyl phosphate analog

1977 ◽  
Vol 16 (11) ◽  
pp. 2825-2829 ◽  
Author(s):  
Joseph. Crea ◽  
Robert. DiGiusto ◽  
Stephen F. Lincoln ◽  
Evan H. Williams
1982 ◽  
Vol 35 (7) ◽  
pp. 1489
Author(s):  
AE Bakas ◽  
AM Hounslow ◽  
SF Lincoln ◽  
NJ Maeji

The three species [UO2{OP(OMe)(NMe2)2}4](ClO4)2, [UO2{OP(OMe)2(NMe)}5] (C1O4)2 and [UO2{OPMe2Ph)]5] (ClO4)2 have been isolated and their CD2Cl2 solutions studied by means of 31P n.m.r. An equilibrium between [UO2L52+ and [UO2L4]2+ exists in solutions of the first two species. In solutions of the third species [UO2L5]2+ predominates and ligand exchange proceeds through a dissociative D mechanism for which kex (285 K), characterizing a single ligand, is 1830 � 250 s-1, ΔH‡ 82.15 � 1.8 kJ mol-1 and ΔS‡ 106 � 16 JK-1 mol-1.


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