Metal chelates of 1,1,1-trifluoro-4-mercapto-4-(2-thienyl)but-3-en-2 one, C4H3SC(SH)=CHCOCF3 (TTMBH), and 1,1,1-trifluoro-4-mercaptopent-3-en-2-one, MeC(SH)=CHCOCF3 (TMPH) have been prepared. Inner complexes of both TTMBH and TMPH were obtained with cobalt(III), nicke1(II), palladium(11), platinum(II), zinc(II), cadmium(11), mercury(11), and lead(II); they are readily soluble in organic solvents. TTMBH gives the spin-free complex Fe(TTMB)3, the copper(II) complex Cu(TTMB)2, and the μ-dioxo-bridgedvanadium(1V) compound V2O2(TTMB)4. Iron(III) and copper(II) oxidize TMPH to the disulphide (TMP)2; however, a polymeric copper(I) complex Cu(TMP) was isolated. The complexing ability of TMPH appears to be weaker than that of TTNBH.