Unprecedented formation of dinuclear macrocyclic complexes by insertion of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-Tcnq) into a C-H bond and subsequent coordination to metal atoms

The complexes [(CpRhCl)-Rh-.(PPh[C6H3-2,6-(MeO)(2)](C6H3-2-O6-OMe)-P,O}] (1a) and [Cp*MCl{PPh2(C6H3-2-O-6-MeO)P,O}] (1b: M = Rh; 3b: M = Ir) with PO chelating coordination react readily with lithium 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane [Li(F-4-tcnq)] to form the dimeric complexes 2a, 2b and 4b by substitution of the H atom adjacent to the metal-O bond with F4-tcnq and coordination through the nitrogen atom of a cyano group to another metal. The Xray crystal structure of 2a is described. Reaction of 1b with F-4-tcne proceeds by an insertion into the C-H bond adjacent to the Rh-O bond.