Zirconium and lanthanide complexes supported by chelating diamido ligands.

摘要

A series of zirconium complexes supported by the chelating diamido ligand (C6F5NHCH2CH2OCH2) 2 (H2(NOON)) have been prepared. These complexes include (NOON)Zr(CH2Ph)2, (NOON)ZrMe2, (NOON)ZrCl 2, and (NOON)ZrCl[N(SiMe3)2]. (NOON)ZrMe 2 and (NOON)ZrCl[N(SiMe3)2] were crystallographically characterized and for all the complexes, the ligand NMR spectra were consistent with a fluxional process occurring in solution. When (NOON)Zr(CH2Ph) 2 was exposed to 435 nm light, a photochemical reaction occurred which resulted in C-F bond activation and the formation of (NOON)ZrF2 and a metallated dimer. When (NOON)ZrCl2 was treated with MAO, it showed modest activity as an ethylene polymerization catalyst.; A series of zirconium complexes supported by 1,4,8,11-tetraazabicyclo[6.6.2]hexadecane (H2(CBC)) have been prepared and characterized. (CBC)Zr(CH 2Ph)N(But)C(H) = CHPh, (CBC)Zr(O-2,6-C6H 3Me2)2, (CBC)Zr(OSi(But)2 H)2, (CBC)Zr(CH2SiMe3)2, (CBC)ZrC4Ph4 were crystallographically characterized and (CBC)Zr(CH2Ph)(O-2,6-C6H3But 2), (CBC)Zr[kappa2((C,O)-OC6H3(6-Bu t)(2-CMe2CH2)], (CBC)ZrCl2. (CBC)ZrCl[N(SiMe 3)2] and (CBC)ZrMe2 were fully characterized. Treatment of (CBC)ZrMe2 with MAO does not result in an active ethylene polymerization catalyst. The metallacycle (CBC)ZrC4Ph4 reacts with thionyl chloride and dichlorophenylphosphine to yield tetraphenylthiophene oxide and pentaphenylphosphole respectively.; Treatment of Yb[N(SiMe3)2]2(OEt 2)2 with H2(CBC) results in the sparingly soluble coordination polymer [(CBC)Yb]n and two byproducts of this reaction were crystallographically characterized. One was the mixed valence salt {lcub}[(mu-CBC)Yb] 3(mu3-O){rcub}+ {lcub}Yb[N(SiMe3) 2]3{rcub}-, while the other was {lcub}[(mu-CBC)Yb] 3(mu3-O){rcub}+I-. In both cases the cation is a trimer of ytterbium (III) ions bridged by an oxygen and three amido nitrogens from the (CBC) ligand.