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

Nicole L Lampland; Jing Zhu; Megan Hovey; Barun Jana; Arkady Ellern; Aaron D Sadow

doi:10.1021/acs.inorgchem.5b00927

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

Inorg Chem. 2015 Jul 20;54(14):6938-46. doi: 10.1021/acs.inorgchem.5b00927. Epub 2015 Jun 25.

Authors

Nicole L Lampland¹, Jing Zhu¹, Megan Hovey¹, Barun Jana¹, Arkady Ellern¹, Aaron D Sadow¹

Affiliation

¹ Department of Chemistry and US Department of Energy Ames Laboratory, Iowa State University, Ames, Iowa 50011, United States.

PMID: 26110352
DOI: 10.1021/acs.inorgchem.5b00927

Abstract

{Bo(M)Cp(tet)}Lu(CH2Ph)2 (1; Bo(M)Cp(tet) = MeC(Ox(Me2))2C5Me4; Ox(Me2) = 4,4-dimethyl-2-oxazoline) was prepared in 95% yield from the reaction of Bo(M)Cp(tet)H and Lu(CH2Ph)3THF3. 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)Cp(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)Cp(tet)}LuNCH2(1-C10H7)]2 in the solid state. The reaction of 1 and NH3B(C6F5)3 affords crystallographically characterized {Bo(M)Cp(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.