Fluorous biphasic catalysis. 2. Synthesis of fluoroponytailed amine ligands along with fluoroponytailed carboxylate synthons, [M(C8F17(CH2)(2)CO2)(2)] (M = Mn2+ or Co2+): Demonstration of a perfluoroheptane soluble precatalyst for alkane and alkene functionalization in the presence of tert-butyl hydroperoxide and oxygen gas

Fluorous biphasic catalysis (FBC) is a relatively new concept for homogeneo us catalysis where the fluorocarbon soluble catalyst resides in a separate phase from the substrate and products. Therefore, separation of the catalys t and the products occurs by a facile decantation process. In this contribu tion, we present the synthesis of new R-f-fluoroponytailed synthons, 2-iodo -1-perfluorooctyl-3-propanol (1), 3-perfluorooctyl-1-propanol (2), and 3-pe rfluorooctyl-1-iodopropane (3), a variety of new R-f-fluoroponytailed ligan ds (4-8), with starting amines, 1,4,7-triazacyclononane, bis-picolylamine, and bis-picolylaminoethylenediamine, as well as new RfMn2+ and RfCo2+ fluor oponytailed carboxylate synthons, [Mn(O2C(CH2)(2)C8F17)(2)] (9), and [Co(O2 C(CH2)(2)C8F17)(2)] (10), where R-f is C8F17. The only totally perfluoralka ne soluble ligand we found was 1,4,7-tris-N-(4,4,5,5,6,6,7,7,8,8,9,9,10,10, 11,11,11-heptadecafluoroundecyl)-1,4,7-triazacyclononane (R(f)TACN, 4), and it was utilized, along with synthons 9 and 10, to generate in situ RfMn2+- R(f)TACN and RfCo2+-R(f)TACN complexes as precatalysts for functionalizatio n of alkanes and alkenes. We will demonstrate that indeed this novel FBC ap proach for the separation of the precatalyst from the substrates and (or) p roducts is viable for oxidation of alkanes and alkenes in the presence of t he necessary oxidants, tert-butyl hydroperoxide (TBHP), and O-2 gas. We wil l also show that these oxidation reactions occur via an autoxidation mechan ism under our FBC conditions, while using electron spin resonance (ESR) tec hniques to ascertain the redox chemistry occurring with the starting mononu clear RfMn2+-R(f)TACN complex.