Dibenzotropylidene phosphanes (TROPPs): synthesis and coinage metal complexes

Dibenzocycloheptatrienyl phosphanes (dibenzotropylidene phosphanes = TROPP(R)) 11a-c may be easily prepared from dibenzocycloheptatrienyl chloride 8 and the secondary phosphanes R2PH [9a: R = Ph; 9b: R = 4-Me-C6H4; 9c: R = cyclohexyl (Cyc)] in good yields. Alternatively, the di(tert-butyl)phosphanyl substituted TROPPBut derivative 4 was obtained along with the phosphane 5 by a mechanistically still unknown rearrangement of a strained phosphorus ylide I. The conformations of these new phosphanes were established by X-ray analyses performed for the compounds TROPPBut 4 and TROPPPh 11a. The R2P moiety is bonded to an axial position of the central seven-membered ring, which adopts a boat conformation. Thereby a rigid concave binding site containing a phosphane and an olefin function is formed, which should allow the synthesis of a wide range of transition metal complexes. In order to test how far the particular shape of the TROPP-type ligands enforces metal-olefin interactions, the coinage metal complexes [(TROPPPh)Cu(mu(2)-Cl)](2), 13, [(TROPPPh)Ag(mu(2)-O2SOCF3)](2), 16, C(TROPPPh)(2)Ag][O3SCF3], 17 and [(TROPPPh)AuCl], 19 were prepared. These were completely characterized by multinuclear NMR experiments in solution and the solid state, as well as by X-ray analyses. The structural and NMR data show that the interaction between the metal center M and the olefin moiety of the TROPP ligand is weak and decreases in the order Cu > Ag > Au. Indeed, for 19 (M = Au) no interaction could be observed. In the silver complex 17, coupling between an Ag nucleus and a proton of a bonded olefin was determined for the first time [J(Ag-109/107, H-1) = 0.4 Hz]. In solution the complexes derived from TROPP-type ligands seem to have an enhanced (kinetic) stability.