Actinide complexes alkoxides

Metallotropic rearrangement, in mercury tri-azenide complexes, 30 41 Metals, see also Heterobimetallics specific element Transition metal complex alkoxides, 15 159-297 of actinides, 15 290-293 of alkali metals, 15 260-263 of alkaline earths, 15 264-266 of aluminium, 15 266-272 of beryllium, 15 264-266 double type, 15 293-294 of gallium, 15 266-272 of lanthanides, 15 290-293 of magnesium, 15 264-266 properties of, 15 260 of transition metals, 15 272-290 trialkylsilyloxides, 15 295-297 of zinc, 15 264-266... 

The actinides have a high degree of specificity for neutral and anionic oxygen-containing organic molecules. The actinide complexes with O -donor ligands that are most widely studied include alkoxides, aryloxides amide, carboxylates, and oxalates. Complexes with alcohols, ethers, esters, ketones, aldehydes, ketoenolates, and carbamates have also been reported. 

It is important to note that efforts to synthesize metal alkoxides and aryloxides (particularly lanthanide and actinide complexes) have sometimes produced unexpected products, incorporating halide or oxide ligands, for example. As a result, some early literature may contain incorrect formulations. ... 

Only one study has suggested the formation of an actinide(IID alkoxide (-OR) compound in which R is an alkyl. A recent investigation of the reactivity of Pu wo-propoxide, prepared in situ from the reaction of Pu[N(SiMe3)2]3 and three equivalents HOPr , indicates that the trivalent alkoxide complex is an effective catalyst in the Meerwein-Ponndorf-Verley reduction of ketones by isopropanol. ... 

Actinide(IV) alkoxide complexes have been reported which are coordinated by a variety of other bulky ligand sets. Uranium(IV) amido compounds are reagents for the preparation of homoleptic uranium(IV) alkoxides as well as mixed alkoxide/amido species. A variety of mixed aryloxide-diethylamide derivatives have been pr ared including (U(NEt2)(0-2,6-Bu 2C6H3)3 and U(NEtp(0-2,6-R7CftH3)3. R = Pr . Bu ). The previously described metallacycle... 

Actinide Alkoxides and Other O-Containing Complexes and Salts... 

Table 5.11 Preparation of Actinide Alkoxides and Related O-Containing Complexes...

Some actinide alkoxide complexes can exist in equilibrium, for example, the homoleptic complex Th2(OCH-/-Pr2)8, obtained from a metallacyclic precursor after treatment with HOCH-/-Pr2 (5.50) ... 

As with the case of the trivalent actinides, the tren, trisamidoamine (NNj), ligand has been used to stabilize An complexes. The preparation of [An(NN) )C1]2 is accomplished by the reaction of the trilithium salt of NNj with AnCLt (An = Th, U). The chloride ligand can be exchanged using metathetical reactions to form AnlTSINjlX (X = Br, I, NR2, OR). Anionic complexes, An(NN))XX (X = OR, X = OR ) can also be formed by addition of alkoxide salts to the neutral species. Complexes of Arf with diamidoamine ligands have also been studied. ... 

Alcohols. Alcohols are among the most common solvate ligands in actinide chemistry (Table 13) historically the hydrated chloride complexes were reacted with alcohol in benzene, and the water of hydration removed by azeotropic distillation of the benzene. More recent examples result from the crystallization of anhydrous halides from alcoholic solvent. Similarly, solvates of alkoxide complexes result from rnetathesis or solvolysis reations in alcohol. The molecular structures of the halides AnCl4(Pr OH)4 (An = Th, U) have been reported,the coordination geometry about the metal is a distorted dodecahedron. 

Actinide(IV) complexes, 1136-1178 alcohols, 1146 aldehydes, 1151 aliphatic amines, 1137 aliphatic hydroxy acids, 1159 alkoxides, 1147 amides, 1161 amine oxides, 1165 ammines, 1137 aqua,1144... 

Actinide(V) complexes, 1179-1187 alcohols, 1180 aliphatic amines, 1179 aliphatic hydroxy acids, 1183 alkoxides, 1181 amides, 1183 amines, 1179 aqua,1179... 

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