Four-coordinate erbium organometallic and coordination complexes: Synthesis and structure

• Published in: Journal of organometallic chemistry Vol. 695; no. 25; pp. 2747 - 2755
• Main Authors: Johnson, Kevin R.D., Côté, Adrien P., Hayes, Paul G.
• Format: Journal Article
• Language: English
• Published: LAUSANNE Elsevier B.V 01.12.2010; Elsevier
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Erbium; Iodide; Lanthanide; Low-coordinate; Physical Sciences; Science & Technology; X-ray crystallography; β-Diketiminato; X-ray crystallography; Iodide; Lanthanide; Low-coordinate; β-Diketiminato; Erbium; ORGANOLANTHANIDE COMPLEXES; F-ELEMENT CHEMISTRY; OLEFIN POLYMERIZATION; beta-Diketiminato; RAY CRYSTAL-STRUCTURE; EPSILON-CAPROLACTONE; BETA-DIKETIMINATO LIGANDS; RING-OPENING POLYMERIZATION; EARTH-METAL COMPLEXES; CATALYTIC-ACTIVITY; SEPARATED ION-PAIRS
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/j.jorganchem.2010.07.033

The synthesis and reactivity of several erbium organometallic and coordination complexes supported by a β-diketiminato ancillary ligand are described. The reaction of ErCl 3(THF) 3.5 with Li L ( L = ArNC(Me)CHC(Me)NAr; Ar = 2,6- i Pr 2-C 6H 3) afforded the dimeric complex Er( L)Cl(μ-Cl) 3Er( L)(THF), 1. Reaction of complex 1 with four equiv of the bulky silylamide LiN(SiMe 3) 2 generated the unexpected four-coordinate adduct dimer [Er( L)N(SiMe 3) 2Cl(μ-(LiN(SiMe 3) 2))] 2, 2. Conversely, reaction of 1 with two or four equiv of LiCH 2SiMe 3 led to the base-free mixed chloro/alkyl species [Er( L)(CH 2SiMe 3)(μ-Cl)] 2, 3, and the four-coordinate dialkyl Er( L)(CH 2SiMe 3) 2, 4, respectively. The protonolysis reactivity of 4 was demonstrated by reaction with [Et 3NH]I to generate Er( L)I 2, 5. By contrast, reaction of complex 1 with trimethylsilyliodide resulted in the formation of ErI 3(THF) 3, 6, through a ligand redistribution process. Compounds 1– 6 were characterized by single crystal X-ray diffraction, multinuclear NMR spectroscopy, FT-IR spectroscopy, solution magnetic susceptibility measurements and CHN combustion analysis. The synthesis and reactivity of a novel series of organoerbium complexes supported by a β-diketiminato ancillary ligand are described. All complexes, including a rare 4-coordinate dialkyl species, have been characterized by X-ray crystallography. [Display omitted]