CHEMISTRY OF POLYFUNCTIONAL MOLECULES .11 4. SYNTHESIS AND STRUCTURE OF AN IONIC AND NON IONIC CYCLIC CARBAPHOSPHAZENE AND OF A COBALT(III)PHOSPHAZENE COMPLEX

Reaction of Ph(2)P double bond N double bond P(Ph(2))double bond N dou ble bond(Phe(2))PCoP(Ph(2))double bond N double bond P(Ph(2))double bo nd N double bond PPh(2) (1) in CH2Cl2 with benzimidazole yields (CH2-P Ph(2)=N-PPh(2)=N-PPh(2))Cl-+(-)([4]Cl-+(-)). The salt [4](+)BPh(4)(-) has been prepared in THF by metathesis of [4]Cl-+(-) with NaBPh(4). De protonation of the cationic ring in [4](+)BPh(4)(-) was accomplished u sing 1,8-diazabicyclo[5.4.0(1,7)] undec-7-ene and resulted in the six- membered carbacyclophosphazene CH=PPh(2)-N=PPh(2)-N=PPh(2) (6). Treati ng 1 with 8-hydroxyquinoline in CH2Cl2 yields the octahedral cis-compl ex (N O)(2)CoP(Ph(2))double bond N double bond P(Ph(2))double bond N d ouble bond PPh(2) (7) (N O = 8-oxyquinolinate group). The compounds [4 ](+)BPh(4)(-), 6 and 7 are characterized by their IR, Raman, P-31{H-1} NMR, C-13{H-1} NMR, H-1 NMR and mass spectra. Crystals suitable for X -ray structure analyses have been obtained for [4](+)BPh(4)(-) and 7x0 .5 CH2Cl2. The colourless plates of [4](divided by)BPh(4)(-) crystalli ze in the triclinic space group P ($) over bar 1, with the lattice con stants a = 1172.7(3), b = 1326.2(3), c = 1806.1(6) pm; alpha = 100.79( 2), beta = 103.71(3): gamma = 108.18(2)degrees. The black blocks of 7x 0.5 CH2Cl2 crystallize in the monoclinic space group P2(1)/c with the lattice constants a = 1159.0(10), b = 2008.9(10), c = 2034.6(12) pm; b eta = 105.86(5)degrees.