ORGANOSULFUR DERIVATIVES OF METAL CARBONYLS .13. SOME TRIFLUOROMETHYLTHIO DERIVATIVES OF METAL CARBONYLS AND CYCLOPENTADIENYLS

Reaction of Mn(CO)5Br with CF3SAg in CH2Cl2 solution gives yellow crystalline [CF3SMn(CO)4]2. However, reaction of Re(CO)5Br with CF3SAg under similar conditions gives not only white [CF3SRe(CO)4]2 but also white CF3SRe(CO)5; the latter compound is converted to [CF3SRe(CO)4]2 upon boiling in cyclohexane. Reaction of C5H5Fe(CO)2I with CF3SAg in acetone solution gives red-brown liquid CF3SFe(CO)2C3H5. Reaction of the π-allyl derivative C3H5Fe(CO)3I with CF3SAg in CH2Cl2 solution gives red liquid CF3SFe(CO)2C5H5. Reaction of C5H5Cr(NO)2Cl with CF3SAg in acetone solution gives yellow-brown crystalline CF3SCr(NO)2C5H5. Reaction of (C5H5)2TiCl2 with CF3SAg does not give a CF3S-Ti derivative. Instead a novel shift of fluorine from carbon to titanium occurs resulting in the formation of yellow (C5H5)2TiF2. The infrared, nmr, and mass spectra of the new compounds are discussed. © 1969, American Chemical Society. All rights reserved.