An Easily Accessible Chiral Carbodiphosphorane and its Coinage Metal Complexes

Herin, the high yielding synthesis of the chiral carbodiphosphorane (3) prepared in a two-step procedure from commercially available (R)-BINAP (([1,1 '-binaphthalene]-2,2 '-diyl)bis(diphenylphosphane), BINAP) and dibromomethane is presented. In the first reaction step, the bis phosphonium salt 1[Br]2 is obtained, which is subsequently deprotonated either with potassium hydroxide to yield the mono phosphonium salt 2[Br], or with potassium hexamethyldisilazide to produce 3. Moreover, coinage metal complexes of 3 were prepared via reaction with CuCl (4Cu, 5Cu, 6Cu), Cu(OTf)& sdot;toluene0.5 (7Cu) or AuCl & sdot; (tht) (5Au, 6Au). The prepared compounds were characterised by NMR- and IR-spectroscopy, mass spectrometry, elemental analysis, single crystal X-ray diffraction and UV/Vis spectroscopy. Photoluminescence emission spectra were obtained for most of the complexes (3, 4Cu, 5Cu, 6Cu and 6Au). Herein, an easy high yield synthesis of an unprecedented chiral carbodiphosphorane (CDP), starting from commercially available (R)-BINAP (([1,1 '-binaphthalene]-2,2 '-diyl)bis(diphenylphosphane), BINAP: )and dibromomethane, yielding the chiral (R)-BINAP-CDP (3) in high yields is presented. The coordination chemistry of 3 is presented by reactions with CuX (X=Cl, OTf) and [AuCl(tht)] with different stoichiometries, yielding different coordination modes. image