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Nucleophilic reactivity of a d(0) molybdenum oxo moiety

Cross, WB; Anderson, JC; Wilson, CS; (2009) Nucleophilic reactivity of a d(0) molybdenum oxo moiety. DALTON T (7) 1201 - 1205. 10.1039/b817745g.

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Abstract

The previously reported complexes [Mo((NBu)-Bu-t)(O)(2,6-Me2C6H3O)(2)(py)] (1) and [Mo((NBu)-Bu-t)(O)(2,6-iPr(2)C(6)H(3)O)(2)(py)] (2) have been shown to contain a nucleophilic oxo ligand. The reaction of 2 and tert-butylacetyl chloride gave the novel complex [Mo((NBu)-Bu-t)(2,6-(Pr2C6H3O)-Pr-i)(2)((O2CCH2Bu)-Bu-t)Cl] (3) in 63% yield as the product of nucleophilic acyl substitution. Complex 1 undergoes a clean reaction with triflic anhydride to give the novel complex [{Mo((NBu)-Bu-t)(2,6-Me2C6H3O)(2)}(mu-O)(mu-OTf)(2)] (4) in 75% yield. Complex 4 appears to be formed from nucleophilic attack of the oxo ligand on triflic anhydride, followed by nucleophilic attack of a second oxo moiety on the cationic intermediate. The solid-state structures of 3 and 4 have been determined by X-ray crystallography. These are rare examples of nucleophilic oxo ligands bound to a d(0) transition metal centre.

Type:Article
Title:Nucleophilic reactivity of a d(0) molybdenum oxo moiety
DOI:10.1039/b817745g
Keywords:WEAKLY COORDINATING ANIONS, ACYL SUBSTITUTIONS, CRYSTAL-STRUCTURES, COMPLEXES, IMIDO, TRIFLUOROMETHANESULFONATE, ANHYDRIDES, INSERTION, TRIFLATE, ACIDS
UCL classification:UCL > School of BEAMS > Faculty of Maths and Physical Sciences > Chemistry

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