CHEMISTRY OF POLYFUNCTIONAL MOLECULES .111. SYNTHESIS AND STRUCTURE OF NOVEL SPIROCYCLIC NICKEL(II) AND PALLADIUM(II) COMPLEXES WITH THE PHOSPHAZENE ANION [PH2P-N-P(PH2)-N-PPH2]-

When anhydroUS MCl2 (M = Ni, Pd) is treated with LiN(PPh2)2 (1) in the molar ratio 1:2 in boiling toluene for 60 hours the new spirocyclic metallaphosphazenes Ph2P-N-P(Ph2)-N-PPh2MPh2P-N-P(Ph2)-N-PPh2 (4a, b; M = Ni, Pd) are obtained by oxidative scrambling of the P-N-P anion in 1. N(PPh2)3 (3), the elemental metals and LiCl are also formed. The compounds 4a, b are characterized by IR, Raman, P-31{H-1} NMR, H-1-NMR, C-13{H-1} NMR, and FD mass spectra. The X-ray crystal structures of 4 a x 1 CH2Cl2 and 4 b x 0,597 CH2Cl2 show that the metals in 4a, b occupy a mid-position between tetrahedral and square planar coordination. Both rings in 4 a, b show a torsion angle of nearly 45-degrees at the spirocyclic metal centre.