Synthesis and characterization of lanthanide complexes with phenalenide and aromatic-fused cyclopentadienyls as ligands




Sun, Jianlong

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The synthesis of yttrium phenalenide complexes 129-132 was achieved by salt metathesis reactions between ligand anions and YCI3. Ytterbium phenalenide complexes 133-137 were synthesized by protonolysis reactions between neutral ligands and Yb[N(SiMe3)2]2(THF)2. The solid state structure of (Pni1Bu)2Yb(THF) 136 reveals a unique n3 bonding pattern, however the electrons of the phenalenide ligand remain delocalized even when bonded to the metal center. Mono-alkyl complexes (PCpR)2Y(CH2SiMe3)(THFSiMe3)(THF) 147-149 (R = Me. Ph. H) and bis-alkyl complexes (PCp*)Y(CH2SiMe3)2(THF) 150 and (sCp)Y(CH2SiMe3)2(THF) 152 were synthesized by direct protonolysis reactions between Y(CH2SiMe3)3(THF)2 and neutral ligands. When treated with phenylsilane, complex 148 generated the crowded hydride dimer [(PCpPh)2Y(u-H)]2 161. Complexes 150 and 152 undergo acid-base. metallation. insertion reactions and polymerization of small substrates. A variable temperature `H NMR study of 150 and 152 at low temperature reveals an equilibrium between 150/152-THF and 1501152. The THF-free complexes. 150/152-THF. appear to undergo inversion of a pyramidal ground state structure to generate a C2 symmetric intermediate. The X-ray structures of 136, 147, 150. 152, (sCp)Y(CH2SiMe3)2(bipy) 154, 161. [PCp*Y(CCSiMe3)(THF)]2(u2-CCSiMe3)2] 167, acetylide cluster 169 and bis-(Me3Si)2Cp yttrium chloride dimer 176 were determined and structural features discussed.



rare earth metals, ligands