Naphthyl substituted Carbodiphosphoranes: Synthesis and Reactivity towards CuCl

Herein we present the two-step synthesis of two new 2-naphthyl substituted Carbodiphosphoranes (CDPs). In the first step either two equivalents of P(Naph)Ph2 (Naph = 2-naphthyl-) and CH2Br2 or P(Naph)Ph2 and [Ph3P(CH2Br)]Br are reacted whereby the symmetrical bis phosphonium salt 1a and the unsymmetric salt 1b are obtained. Subsequently, the CDPs 2a and 2b where prepared by deprotonation with two equivalents of potassium hexamethyldisilazanide. After isolation, the coordination chemistry of 2a and 2b towards CuCl is explored where, depending on educt stoichiometry, mononuclear (3a, 3b) and dinuclear compounds (4a, 4b) are obtained. All prepared compounds were characterised by NMR spectroscopy, mass spectrometry and elemental analysis. For most compounds single crystal X-ray diffraction data (1a, 1b, 2a, 3b, 4a, 4b) was collected and UV/Vis spectra (2a, 2b) were measured. Moreover, photoluminescence emission spectra were obtained for the 2-naphthyl substituted CDPs (2a and 2b) and the copper complexes (3a, 3b, 4a, 4b).