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The reaction of ZrCI, with (Me,Si),NPPh,NSiMe, 1 yields the four-membered heterocycle (hCI,(Me,SiNPPh,hSiMe,)). An improved synthesis of the aminoiminophosphorane 1 is described. The compound TiCI, reacts with Me,SiOPPh,NSiMe, unexpectedly with elimination of all Me,Si groups to yield the eight-membered heterocycle ({TiCI,(OPPh,N)},). A vanadium-containing dimetallacyclophosphazene ({VCl,( NPPh,N)},) has been synthesised from (VCI,( NSiMe,)) and CIPPh,NSiMe,. The X-ray structures of (hCI,( Me,SiNPPh,hlSiMe,))*MeCN and ({TiCI,- (OPPhZN)},)*4MeCN have been determined. While the cyclic Zr-N distances in the former have to be considered as single bonds, the short Ti-N of the latter (almost planar) suggest double-bond character.

journal of the chemical society. dalton transactions

Four- and eight-membered cyclic phosphazene derivatives of zirconium, titanium and vanadium. Crystal structures of the complexes [ZrCl3(Me3SiNPPh2NSiMe3)]·MeCN and [{TiCl2(OPPh2N)}2]·4MeCN