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Gas-phase basicities of six fluorinated acetones have been determined from proton transfer equilibrium and bracketing experiments with ion cyclotron resonance spectroscopy. A very regular decrease in proton affinity of 6.1 ± 0.4 kcal mol"1 for each successive fluorine substituent is found. This result is interpreted in terms of a substituent effect which is almost purely inductive and correlates extremely well with electronegativity of the methyl substituents. In addition, a small stabilizing interaction of 2-3 kcal mol"1 is revealed in each of the protonated fluoroacetones due to formation of an intramolecular hyrogen bond.

Oxidation of ( v -C ~H ~) ~Vwith C5H5N0 in toluene gives (r)-C5H5)4V4(p3-0)4 and (q-C5H5)5(0)V6(p3-O)8 (1) whereas oxidation with Me3N0 gives {(q-C5H5)5V6(~3-0)8}2{(p-o)2V(r)-C5H~)(NMe3)2} and {(q-C5H5)5V~(p3-0)8}2(p-o) (2); the structures of (1) and ( 2) have been established by X-ray crystallography.

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