1309569-83-2Relevant academic research and scientific papers
Group 4 metallocene complexes with pendant nitrile groups
Pinkas, Ji?í,Gyepes, Róbert,Kubi?ta, Ji?í,Horá?ek, Michal,Lama?, Martin
, p. 2364 - 2372 (2011/06/26)
The preparation of a new functionalized cyclopentadienyl ligand bearing a nitrile pendant substituent, (C5H4CMe2CH 2CN)- is reported. The corresponding lithium salt of this ligand (1) was prepared by the reaction of in situ lithiated acetonitrile with 6,6-dimethylfulvene. The ligand was subsequently utilized for the synthesis of group 4 metal complexes [(η5-C5H4CMe 2CH2CN)2MCl2] (M = Ti, 2; M = Zr, 3; M = Hf, 4), [(η5-C5H5) (η5-C5H4CMe2CH 2CN)MCl2] (M = Ti, 7; M = Zr, 8), and [(η5- C5Me5) (η5 C5H 4CMe2CH2CN)2ZrCl2] (9). Alternative route to 2 comprised the preparation of half-sandwich complex [(η5-C5H4CMe2CH 2CN)TiCl3] (6). The prepared compounds were characterized by common spectroscopic methods and the solid state structures of complexes 2, 3, 4, 7, and 9 were determined by the single-crystal X-ray diffraction analysis. In addition, compound 7 was converted to the corresponding dimethyl derivative [(η5-C5H5) (η5-C 5H4CMe2CH2CN)TiMe2] (10) and also treated with the chloride anion abstractor Li[B(C6F 5)4] to generate the cationic complex with the coordinated nitrile group, as suggested by the NMR spectroscopy. A formation of yet another cationic complex was observed upon treating compound 10 with (Ph 3C)[B(C6F5)4].
