Synthesis of Partially Fluorinated Alkyl Triflates by Electrochemical Fluorination (Simons Process).

A scalable straightforward synthesis of monofluoro- and difluoromethyl triflate CF SO OCH F (M ) and CF SO OCHF (M ) through electrochemical fluorination (ECF, Simons process) of methyl triflate M in anhydrous hydrogen fluoride at nickel anodes is presented. The ECF method is also feasible for the preparation of the deuterated analogues CF SO OCD F (M ) and CF SO OCDF (M ). Surprisingly, no H/D exchange occurs during ECF of CF SO OCD (M ); this provides further evidence for a NiF /NiF -mediated ECF mechanism.

Stable and Storable N(CF ) Transfer Reagents.

Fluorinated groups are essential for drug design, agrochemicals, and materials science. The bis(trifluoromethyl)amino group is an example of a stable group that has a high potential. While the number of molecules containing perfluoroalkyl, perfluoroalkoxy, and other fluorinated groups is steadily increasing, examples with the N(CF ) group are rare.

Cyclometalated Platinum(II) Cyanometallates: Luminescent Blocks for Coordination Self-Assembly.

A family of cyanide-bridged heterometallic aggregates has been constructed of the chromophoric cycloplatinated metalloligands and coordinatively unsaturated d fragments {M(PPh)}. The tetranuclear complexes of general composition [Pt(C^N)(CN)M(PPh)] [C^N = ppy, M = Cu (1), Ag (2); C^N = tolpy (Htolpy = 2-(4-tolyl)-pyridine), M = Cu (4), Ag (5); C^N = Fppy (HFppy = 2-(4, 6-difluorophenyl)-pyridine), M = Cu (7), Ag (8)] demonstrate a squarelike arrangement of the molecular frameworks, which is achieved due to favorable coordination geometries of the bridging ligands and the metal ions. Variation of the amount of the ancillary phosphine (for M = Ag) afforded compounds [Pt(C^N)(CN)Ag(PPh)] (C^N = ppy, 3; C^N = tolpy, 6); for the latter one an alternative cluster topology, stabilized by the Pt-Ag metallophilic and η-C(C^N)-Ag bonding, was observed.