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Piano-Stool Lutetium Amido and Imido Compounds Supported by a Constrained Bis(oxazoline)cyclopentadienyl Ligand

TitlePiano-Stool Lutetium Amido and Imido Compounds Supported by a Constrained Bis(oxazoline)cyclopentadienyl Ligand
Publication TypeJournal Article
Year of Publication2015
AuthorsLampland, NL, Zhu, J, Hovey, M, Jana, B, Ellern, A, Sadow, AD
JournalInorganic Chemistry
Volume54
Pagination6938-6946
Date Published07
Type of ArticleArticle
ISBN Number0020-1669
Accession NumberWOS:000358549300031
Keywordsactivation, alkynes, benzene, bond activation, c-h activation, complexes, intermolecular hydroamination, intramolecular hydroamination, mechanism, polymerization catalysts, Zirconium
Abstract

{Bo(M)Cp(tet)}Lu(CH2Ph)(2) (1; Bo(M)Cp(tet) = MeC-(Ox(Me2))(2)C5Me4; Ox(Me2) = 4,4-dimethyl-2-oxazoline) was prepared in 95% yield from the reaction of Bo(M)C(p)(tet)H and Lu(CH2Ph)(3)THF3. Compound 1 reacts with 1 or 2 equiv of H2NCH2R (R = C6H5, 1-C10H7) to give the corresponding imido complexes [{Bo(M)Cp(tet)}LuNCH2R](2) (R = C6H5 (2a), 1-C10H7 (2b)) or amido complexes {Bo(M)C(p)(tet)}Lu(NHCH2R)(2) (R = C6H5 (3a), 1-C10H7 (3b)). Once isolated, the imido species are insoluble in nonprotic organic solvents. Crystallographic characterization reveals dimeric [{Bo(M)C(p)(tet)}-Lu(NCH2(1-C10H7)](2) in the solid state. The reaction of 1 and NH3B(C6F5)(3) affords crystallographically characterized {Bo(M)C(p)(tet)}Lu{NHB(C6F5)(2)}C6F5. This species is proposed to form via a transient lutetium imido, which undergoes C6F5 migration to the lutetium center.

DOI10.1021/acs.inorgchem.5b00927
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