Fluorous biphasic catalysis.: 2.: Synthesis of fluoroponytailed amine ligands along with fluoroponytailed carboxylate synthons, [M(C8F17(CH2)2CO2)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 homogeneous catalysis where the fluorocarbon soluble catalyst resides in a separate phase from the substrate and products. Therefore, separation of the catalyst and the products occurs by a facile decantation process. In this contribution, we present the synthesis of new R-f-fluoroponytailed synthons, 2-iodo-1-perfluorooctyl-3-propanol (1), 3-perfluorooctyl-1-propanol (2), and 3-perfluorooctyl-1-iodopropane (3), a variety of new R-f-fluoroponytailed ligands (4-8), with starting amines, 1,4,7-triazacyclononane, bis-picolylamine, and bis-picolylaminoethylenediamine, as well as new RfMn2+ and RfCo2+ fluoroponytailed carboxylate synthons, [Mn(O2C(CH2)(2)C8F17)(2)] (9), and [Co(O2C(CH2)(2)C8F17)(2)] (10), where R-f is C8F17. The only totally perfluoralkane 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 functionalization of alkanes and alkenes. We will demonstrate that indeed this novel FBC approach for the separation of the precatalyst from the substrates and (or) products is viable for oxidation of alkanes and alkenes in the presence of the necessary oxidants, tert-butyl hydroperoxide (TBHP), and O-2 gas. We will also show that these oxidation reactions occur via an autoxidation mechanism under our FBC conditions, while using electron spin resonance (ESR) techniques to ascertain the redox chemistry occurring with the starting mononuclear RfMn2+-R(f)TACN complex.