Synthesis of allyl-transition metal complexes by phase transfer catalyzed reactions of metal carbonyl halides: III. Considerations of the mechanisms |
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Authors: | Dorothy H. Gibson Wen-Liang Hsu Fahim U. Ahmed |
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Affiliation: | Department of Chemistry, University of Louisville, Louisville, Kentucky 40292 U.S.A. |
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Abstract: | Mechanisms are proposed for the hydroxide ion-initiated reactions of metal carbonyl halides which lead to allyl-transition metal complexes under phase transfer conditions. Evidence is presented for intermediate anionic metallocarboxylic acids in reactions leading to η3-allyl products of molybdenum, iron, ruthenium and manganese, whereas η1 complexes are shown to result from halide displacement reactions in which simple metal carbonyl anions are generated. In some cases phosphorus-containing ligands inhibit the hydroxide-promoted reactions of metal carbonyl halides with allyl bromide; a rationale involving decreased acidity of the carbonyl ligands is presented. Syntheses of η3-C3H5Mn(CO)3P(OCH3)3 and η3-C3H5Mn(CO)2[P(OCH3)3]2 by phase transfer catalysis are also described. |
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