CHEMISTRY OF POLYFUNCTIONAL MOLECULES - 1 28 - SYNTHESIS AND CRYSTAL-STRUCTURE OF N,N,N',N'',N''-PENTAMETHYLDIETHYLENE-TRIAMINE COCOORDINATED SODIUM BIS(DIPHENYLPHOSPHANYL)AMIDE AND ABOUT A [12]-CROWN-4-ETHER DERIVATIVE

The metalation of bis(diphenylphosphanyl)amine [HN(PPh2)(2) (4)] with NaH in the presence of N,N,N',N '',N ''-pentamethyl-diethylene-triamin e [PMDTA (2)] at 105 degrees C in toluene affords the monomeric yellow sodium complex [(Ph2P)(2)NNa . PMDTA] (5). X-ray analysis reveals tha t the coordination sphere of the sodium ion consists of the chelating triamine ligand 2 and [N(PPh2)(2)](-) as N- and monodentate P-donor. A dditional weak eta(1) C-contacts to 2 and [N(PPh2)(2)](-) are discusse d. In the presence of [12]-crown-4-ether, HN(PPh2)(2) and NaH react to the dimeric yellow-green complex [{(Ph2P)(2)NNa}(2){[12]-crown-4}(5)] (6). The compound 6 crystallizes in thin needles, but they are not su itable for X-ray analysis. The dimeric non ionic structure of 6 has be en confirmed by mass spectroscopy and conductivity measurements.