PERHALOARYLMETAL CHEMISTRY .4. FORMATION AND PROPERTIES OF SOME ORGANONICKEL DERIVATIVES OF TYPE (PI-C5H5)(R2R'P)(R'')NI

A series of air-stable organonickel complexes of the type (π-C5H5)(R2R′P)(R″)Ni (R = phenyl, R′ = methyl or phenyl, and R″ = methyl, phenyl, or perhalophenyl) containing σ-bonded organic substituents has been obtained from organonickel halides (π-C5H5)(R2R′P)(R″)NiCl and appropriate organolithium reagents. Analogous trifluoromethyl and heptafluoropropyl derivatives have been prepared from reactions of the respective perfluoroalkyl iodides with bis(π-cyclopentadienyl)dicarbonyldinickel followed by treatment with triphenylphosphine. The perhalogenated derivatives have been found to exhibit enhanced thermal, oxidative, and hydrolytic stabilities compared to their hydrocarbon analogs. σ-Bonded methyl complexes of this series readily undergo insertion with sulfur dioxide to form S-methylsulfinato derivatives. Trends in the proton nmr spectra of these σ-bonded organonickel complexes are discussed. © 1969, American Chemical Society. All rights reserved.