Yttrium and Aluminum Alkyl Complexes of a Rigid Bis-Anilido NON-Donor Ligand: Synthesis and Hydroamination Catalysis

• Published in: Organometallics Vol. 36; no. 8; pp. 1601 - 1608
• Main Authors: Motolko, Kelly S. A, Emslie, David J. H, Jenkins, Hilary A
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 24.04.2017; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Physical Sciences; Science & Technology; H BOND ACTIVATION; ALKENES; PARA-POSITION; OLEFIN POLYMERIZATION CATALYSIS; METAL-CATALYSTS; INTERMOLECULAR HYDROAMINATION; ASYMMETRIC HYDROAMINATION; INTRAMOLECULAR HYDROAMINATION; BEARING DIFFERENT SUBSTITUENTS; ETHYLENE POLYMERIZATION
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/acs.organomet.7b00156

The palladium-catalyzed coupling of 4,5-dibromo-2,7-di-tert-butyl-9,9-dimethylxanthene (XBr2) with 2 equiv of 2,4,6-triisopropylaniline afforded the proligand 4,5-bis­(2,4,6-triisopropylanilino)-2,7-di-tert-butyl-9,9-dimethylxanthene (H2XN2), and reaction of H2XN2 with [Y­(CH2SiMe2R)3(THF)2] (R = Me, Ph) produced the monoalkyl yttrium complexes [(XN2)­Y­(CH2SiMe2R)­(THF)] (R = Me (1a), Ph (1b)). Neutral 1a showed near-zero ethylene polymerization activity (1 atm, 20 and 80 °C), and in the presence of AlMe3, 1a converted to [(XN2)­Y­{(μ-Me)2AlMe2}­(THF)] (2). Compound 2 is thermally robust, and transfer of the XN2 ligand from yttrium to aluminum was not observed even at elevated temperatures. However, [(XN2)­AlMe] (3) was accessible via the reaction of H2XN2 with AlMe3, demonstrating the ability of the wide-bite-angle XN2 ligand to coordinate to much smaller aluminum­(III). Neutral 1a proved to be highly active for both intra- and intermolecular hydroamination with various substrates, yielding Markovnikov products in the intermolecular hydroamination reactions with 1-octene.