CHEMISTRY OF POLYFUNCTIONAL MOLECULES, 108[1] TETRAHEDRAL COPPER(I) CHELATE COMPLEXES WITH THE LIGANDS BIS(DIPHENYLPHOSPHINO)AMINE AND BIS(DIPHENYLPHOSPHINO)METHANE

Reaction of [Cu(PPh3)2(NO3)] (1) in acetone with bis(diphenylphosphino)amine (dppa, 2) yields [Cu(dppa)(PPh3)2]+NO3- (3a). [Cu(dppa)(PPh3)2]+PF6- (3b) has been synthesized by metatheses of 3a with NH4PF6. The salt [Cu(dppm)(PPh3)2]+PF6- (5b) has been prepared by an one batch reaction of [Cu(PPh3)2(NO3)] (1), bis(diphenylphosphino)methane (dppm, 4) and NH4PF6 in methanol, because [Cu(dppm)(PPh3)2]+NO3- (5a) could not be isolated by the direct reaction of 1 with 4. The IR, Raman, P-31 {H-1} NMR, H-1 {P-31} NMR as well as the conductivity data are reported and discussed together with the X-ray crystal structure of 3a . 1.8 (CH3)2CO. The structure consists of copper atoms coordinated tetrahedrally by two PPh3 ligands and the chelating dppa ligand and features a highly strained four-membered ring. The distorted tetrahedral cations are hydrogen bridged to the nitrate anions. The colourless needles of 3a . 1.8 (CH3)2CO crystallize in the monoclinic space group C2/c, with the lattice constants a = 4189.2(27); b = 1223.7(8); c = 2717.8(15) pm; beta = 113.16(4)-degrees.