I. Synthesis and Characterization of the New Cyclopentadienyl Vanadium Tricarbonyl Hydride and Methyl Anions and their Reactions with Organic Substrates. II. Monomeric Organometallic Dianions

Author: Kinney, Robert James

Year: 1978

Degree: Dissertation (Ph.D.)

Advisor: Bergman, Robert G.

Committee Member: Unknown, Unknown

Option: Chemistry

DOI: 10.7907/pygb-k537

Abstract

The new anionic cyclopentadienyl vanadium tricarbonyl complexes, (n5C5H5)V(CO)3R-, (R=H,CH3),have been isolated as the phosphineminium salts. (n5C5H5)V(CO)3H- reacts with alkyl (primary, secondary, and tertiary), vinyl and aryl bromides at room temperature in THF to replace bromine with hydrogen. A gem-dibromocyclopropane was reduced to the mono-bromide, and acid chlorides were converted to aldehydes with (n5C5H5)V(CO)3H-. Primary alkyl iodides react more rapidly than the bromides and aklyl chlorides do not react at all. Alkyl tosylates react much slower than the corresponding bromides. Carbon radicals and (n5C5H5)V(CO)3Br- as the kinetic organometallic product imply a radical chain mechanism for these reactions.

The reactions of (n5C5H5)V(CO)3CH-3 and alkylbromides and acyl chlorides do not produce new carbon-carbon bonds .

Attempts to prepare the dianious RM(CO)2-3, M = Cr, Mo; R = norbornadiene and M = Mo; R = cyclooctatetraene were not successful.

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