Date of Award
Union College Only
Bachelor of Science
Studies on the reactivity of many transition metal carbonyl complexes with various acetylenes have generated significant interest in the field of organometallic chemistry, but little effort has been put forth to make use of these compounds as genuine organic reagents. Most metal carbonyl compounds generate both organic and organometallic products, where oxidative cleavage becomes necessary to obtain the organic moiety. (35-c5H5)v(CO)4 is an oxygen-sensitive carbonyl complex which has been shown to thermally react with bis-(pentafluorophenyl)acetylene to produce cyclic carbonyl compounds in high yield, particularly the quinone derivative, with few organometallic products. The thermal reactivity of (35-c5H5)v(CO)4 is characterized with various symmetrically and non-symmetrically substituted acetylenes, wiU, emphasis placed on the effect of electron-donating and withdrawing substituents on the alkyne. It was found that in general, acetylenes with electron-donating substituents such as 3-hexyne, bis-(trimethylsilyl)acetylene, and 2-butyne-1,4-diol will not react with (35-c5H5)v(CO)4 to form organic carbonyl compounds. Acetylenes with electron-withdrawing substituents were found to react readily with this vanadium compound to form a variety of cyclic structures, including cyclopentadienones, quinones, tropones, and substituted benzene derivatives. Acetylenes in this catagory include dimethylacetylene dicarboxylate, diphenylacetylene, and pentafluorophenyl phenyl acetylene. Catalytic activity is suggested in certain instances for 35-cyclopentadienyltetracarbonylvanadium.
Newbold, Ronald C., "The Preparation of Cyclic Organic Carbonyl Compounds from 25-Cyclopentadienyltetracarbonylvanadium and Substituted Acetylenes" (1984). Honors Theses. 1899.