Jane V. Zeile

Reactions of Coordinated Molecules : I. The oxidation of transition metal carbenoid complexes by iodosobenzene; a comparative study

Abstract The reaction of transition metal carbenoid complexes with oxidizing agents results in the oxidation of the carbenoid ligand forming the corresponding carboxylic acid derivative. A study of this reaction using pyridine- N -oxide, ceric ammonium nitrate and iodosobenzene as the oxidants reveals that the yield of the carboxylic acid derivative is affected significantly by the solvent medium. Oxidations using pyridine- N -oxide in tetrahydrofuran solution generally afford the organic acid derivatives in good to excellent yields. Iodosobenzene is a selective oxidant affording the greatest yield of ethylene carbonate and it is the first oxidant reported to oxidize an amino-carbenoid complex to the corresponding amide. This oxidation reaction represents a convenient and rapid chemical method for the characterization of carbenoid complexes.

Reactions of coordinated molecules XI. The reaction of the rhenium tetracarbonyl metallo-acetylacetone complex with hydrazines ☆

The reaction of the rhenium tetracarbonyl metallo-acetylacetone molecule, cis -(OC) 4 Re[C(CH 3 )O⋰H⋰O(CH 3 )C], with hydrazine, methylhydrazine and phenylhydrazine affords the corresponding acetyl-amine complexes, cis -(OC) 4 - Re(COCH 3 )(NH 2 R), where R = H, CH 3 , or C 6 H 5 , and acetonitrile. The reactions were followed by proton NMR at 36°C. The half-lilfe of the reaction with phenylhydrazine was 8.67 minutes while the other two hydrazines gave complete reaction within 30 seconds. The X-ray molecular structure determination of the acetyl-aniline complex is reported.

Reactions of coordinated molecules : III. Alkoxy substituent exchange reactions on a cyclic ligand☆

Abstract The extraction of an ethoxide anion from a β-diethylacetal-acyl ligand of a neutral organometallic molybdenum complex affords a cationic complex having a cyclic ligand which is described best as a metal-stabilized oxonium ion. This ligand has an unusually reactive saturated carbon atom which reacts with a variety of alcohols and with ethanethiol via an alkoxy group exchange reaction affording a differently substituted cyclic ligand. The oxidization of the metal—ligand bond in the initial complex forms 4-ethoxy-γ-butyrolactone and, therefore, it is a precursor for the preparation of a variety of 4-substituted-γ-butyrolactones. The reaction of this complex with sodium methoxide and dimethyl sulfoxide is discussed, also.