Insertion von Diphenylcarbodiimid in die Zr–P-Bindung von Cp′2Zr(Cl){P(SiMe3)2} (Cp′ = C5H4Me); Molekülstruktur von / Insertion of Diphenylcarbodiimide into the Zr–P Bond of Cp′2Zr(Cl){P(SiMe3)2} (Cp′ = C5H4Me);

Abstract

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 diphenylcarbodiimide with insertion of the heterocumulene into the Zr–P bond to give (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) Å, 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) Å, β = 95.32(4)°, space group P21/n (No. 14), Ζ = 4, 6408 observed independent reflexions, R = 6.2%). The crystal structure of 3 revealed η2-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) Å, Zr–N 2 2.348(5) Å). The ligand can not be obtained from the reaction of Li(THF)2P(SiMe3)2 with diphenylcarbodiimide, which instead affords