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Dinuclear Copper(I) Complexes Featuring Metal-Metal Interactions and a μ2-Bridging Phosphane With Additional Olefinic
Zhongshu Li1, Daniel Himmelbauer2, Jan Oswald2
1LIFM, IGCME, School of Chemistry, Sun Yat-Sen University, Guangzhou, China.
None:
The molecule Ptrop3 contains in each trop unit (trop = dibenzo[a,d]cyclohepten-5-yl) a rigid central seven-membered ring with an olefinic binding site making Ptrop3 potentially a tetradentate ligand. Nevertheless, in mononuclear CuI complexes, [Cu(Ptrop3)X] [X = Cl (2), OTf (3), BF4 (4')], this phosphane behaves mainly as a highly bulky ligand (cone angle approx. 250 °) and the interactions between CuI center and the C═Ctrop units are remarkably weak, such as in other related Cu trop-type complexes. The reaction of [Cu(Ptrop3)(OTf)] with Cu+ sources allows the preparation of dinuclear complexes [Cu2(μ2-Ptrop3)(μ2-X)]+ (X = Cl, OTf, TFA), which contain a μ2-bridging P center and in which the interaction between the CuI 2 core and the olefins is significantly enhanced. Experimental investigations and DFT calculations indicate that the uptake of a Cu+ ion by the mononuclear complex [Cu(Ptrop3)(OTf)] (3) is a kinetically and thermodynamically favorable process.
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