INSERTION OF DIPHENYLCARBODIIMIDE INTO THE ZR-P BOND OF CP'2ZR(CL)(P(SIME3)2)(CP'=C5H4ME) - CRYSTAL-STRUCTURE OF CP'2ZR[N(PH)C(P(SIME3)2(N(PH)](CL)

The reaction Of Cp'2ZrCl2 (1) (Cp' = C5H4Me) with Li(THF)2P(SiMe3)2 yields the zirconoocene monophosphido compleX Cp'2Zr(Cl){P(SiMe3)2} (2) in good yield. 2 reacts with diphenvlcarbodiimide with insertion of the heterocumulene into the Zr-P bond to give CP'2Zr[N(Ph)C{P(SiMe3)2}N(Ph)](Cl) (3). 2 and 3 were characterized spectroscopically (IR, NMR), and an X-ray structure determination was carried out on 1 and 3 (crystal data: 1, a = 6.803(3), b = 12.008(6), c = 15.480(12) angstrom, space group Pnma (No. 62), Z = 4, 1685 observed independent reflexions, R = 5.4%, 3, a = 9.210(7), b = 11.491(13), c = 31.279(15) angstrom, beta = 95.32(4)-degrees, space group P2(1)/n (No. 14), Z = 4, 6408 observed independent reflexions, R = 6.2%). The crystal structure of 3 revealed eta2-bonding (N,N') of the phosphaguanidene ligand N(Ph)C{P(SiMe3)2}N(Ph)- to the Zr atom (Zr-N 1 2.309(5) angstrom, Zr-N2 2.348(5) angstrom). The ligand can not be obtained from the reaction of Li(THF)2P(SiMe3)2 with diphenylcarbodiimide, which instead affords Li(THF)NPhC{N(SiMe3)Ph} PC{ N(SiMe3)Ph}NPh.