Zirconium and lanthanide complexes supported by chelating diamido ligands

A series of zirconium complexes supported by the chelating diamido ligand (C6F5NHCH2CH20CH2)2(H2(NOON)) have been prepared. These complexes include (NOON)Zr(CH2Ph)2, (NOON)ZrMe2, (NOON)ZrC12, and (NOON)ZrC1[N(SiMe3)2]. (NOON)ZrMe2 and (NOON)ZrC1[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)2was exposed to 435 nm light, a photochemical reaction occurred which resulted in C-F bond activation and the formation of (NOON)ZrF2and a metallated dimer. When (NOON)ZrC12was treated with MAO, it showed modest activity as an ethylene polymerization catalyst. A series of zirconium complexes supported by l , 4 , 8 , l l - tetraazabicyclo[6.6.2]hexadecane (H2(CBC)) have been prepared and characterized. ( C B C > Z ~ ( C H ~ P ~ ) N ( B U ' ) C ( H ) = C ( HC PB ~C , ) Z r ( O - 2 , 6 - C 6 H 3 M e 2 ) 2 , ( c B c ) z ~ ( o s ~ ( B u ' ) ~ H ) ~ , (CBC)Zr(CH2SiMe3)2, (CBC)ZrC4Ph4 were crystallographically characterized and (cBc)z~(cH~P~)(o-2,6-c~H~Bu'~), (CBC)Z~[K~(C,O)-OC~H~(~-RU')(~-CM~~CH~)] (CBC)ZrC12, (CBC)ZrC1[N(SiMe3)2] and (CBC)ZrMe2 were fully characterized. Treatment of (CBC)ZrMe2 with MA0 does not result in an active ethylene polymerization catalyst. The metallacycle (CBC)ZrC4Ph4reacts with thionyl chloride and dichlorophenylphosphine to yield tetraphenylthiophene oxide and pentaphenylphosphole respectively. Treatment of Yb[N(SiMe3)2]2(0Et2)2with H2(CBC) results in the sparingly soluble coordination polymer [(CBC)Yb], and two byproducts of this reaction were crystallographically characterized. One was the mixed valence salt { [ ( ~ - c B c ) Y ~ ] ~ ( ~ ~ - o))'{Y~[N(s~M~~)~w]~h}il-e,the other was { [ ( p - ~ ~ ~ ) ~ b-]o3)}(+pI-.3In both cases the cation is a trimer of ytterbium (111) ions bridged by an oxygen and three amido nitrogens from the (CBC) ligand.