RESUMO
(BCHT-NCN)H3 (1) [1,6-bis(methylene(bis-2,6-diisopropylaniline)(benzo)cycloheptatriene)] was synthesized by nucleophilic substitution treating 1,6-bis(methylenebromide)(benzo)cycloheptatriene with 2 equiv of Li[2,6-iPr2C6H3NH], Li[Dipp-NH]. Triple deprotonation of (BCHT-NCN)H3 (1) using n-BuLi yields the deprotonation product [(BCHT-NCN)Li3] (2), which crystallizes as a dimer [{[BCHT-NCN]Li3(Et2O)2}2] (2)2. Coordination compounds of the trianionic pincer ligand were obtained with SnCl2, YCl3(THF)3.5, and HfCl4(THF)2: [(BCHT-NCN)SnLi] (3), [(BCHT-NCN)Y(THF)2] (4), [(BCHT-NCN)HfCl2][Li(THF)4] (5), respectively. A hafnium hydride complex [(BCHT-NCN)HfH(HBEt3)][K(Et2O)2] (6) was isolated after reaction of 5 with K[HBEt3]. A MeNHC substitution product [(BCHT-NCN)HfCl(MeNHC)] (7) was synthesized treating compound 5 with MeNHC at rt. Following an n-BuLi reaction of 7 gives an alkyl complex [(BCHT-NCN)Hf(n-Bu)(MeNHC)] (8). Thermolysis of 7 yields the isomerization product [(BCHT-NCN#)HfCl(MeNHC)] (9), which was transferred into a methyl complex [(BCHT-NCN#)HfMe(MeNHC)] (10) upon treatment with MeMgBr. Hydride abstraction from complex 9 leads to a cationic complex [(BCHT-NCN+)HfCl(MeNHC)][Al(OtBuF)4] (11).
