A new mode of reactivity for pyridine N-oxide: C-H activation with uranium(IV) and thorium(IV) bis(alkyl) complexes
Jaime A Pool1, Brian L Scott, Jaqueline L Kiplinger
1Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM 87545, USA.
Abstract:
Uranium(IV) and thorium(IV) bis(alkyl) complexes of the type (C5Me5)2AnR2 (An = U, Th; R = CH3, CH2Ph) activate the sp2 and sp3 hybridized C-H bonds in pyridine N-oxide and lutidine N-oxide to produce the corresponding cyclometalated complexes, (C5Me5)2An(R)[eta2-(O,C)-ONC5H4] and (C5Me5)2An(R)[eta2-(O,C)-ON-2-CH2-5-CH3-C5H3]. These provide rare examples of C-H activation chemistry mediated by actinide metal centers. This chemistry is in contrast to the known oxygen atom transfer reactivity patterns of pyridine N-oxides with oxophilic metal complexes and constitutes a new mode of reactivity for pyridine N-oxides.
More Related Videos
Related Concept Videos
Acid Halides to Ketones: Gilman Reagent
As shown below, the mechanism proceeds in two steps. First, one of the alkyl groups of the reagent acts as a nucleophile and attacks the acyl carbon of the acid chloride to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen double...
Preparation of Nitriles
Nitriles to Carboxylic Acids: Hydrolysis
Nitriles to Ketones: Grignard Reaction
The mechanism begins with a nucleophilic attack by the Grignard reagent...
Diazonium Group Substitution: –OH and –H
Acid Halides to Alcohols: Grignard Reaction
Grignard reagents are a source of carbanions and function as nucleophiles. The mechanism begins with the nucleophilic attack by the carbanion at the carbonyl carbon of the acid halide to form a tetrahedral intermediate. Next, the carbonyl group is re-formed, and the halide ion departs,...


