The amino-substituted phosphazene P3N3(NHCy)(6) 1 reacts as a multiprotic a
cid undergoing full deprotonation in the presence of Me3Al and Et2Zn, respe
ctively, which results in the formation of multinuclear metal phosphazenate
s: Trimethyl aluminium deprotonates 1 with evolution of six equivalents of
methane to give the pentanuclear organoaluminium complex [(thfMeAl)(Me2Al)(
4){P3N3(NCy)(6)}] 2. Diethylzinc deprotonates 1 yielding the hexanuclear zi
nc complex [(EtZn)(6){P3N3(NCy)(6)}] 3. The higher homologue P4N4(NHCy)(8)
4 reacts with diethylzinc undergoing sixfold deprotonation giving the hexan
uclear complex [(Etzn)(6){P4N4(NHCy)(2)(NCy)(6)}] 5, where two NH functions
remain protonated. All three metal complexes 2, 3 and 5 are soluble in apr
otic organic solvents. The highly charged phosphazenate ligands contain thr
ee and four PN4 tetrahedra which are fused in a corner-sharing manner formi
ng P3N3 and P4N4 ring structures, respectively. These are isoelectronic wit
h meta-silicate anions, but in addition equiped with organic groups at term
inally arranged N atoms. Both phosphazenate ligands contain various coordin
ation sites and show a high flexibility of their central P-N ring conformat
ion toward the complexed organometallic framework.