Insights into the decomposition pathway of a lutetium alkylamido complex via intramolecular C–H bond activation
Knott, J. P., Hänninen, M. M., Rautiainen, M., Tuononen, H., & Hayes, P. G. (2017). Insights into the decomposition pathway of a lutetium alkylamido complex via intramolecular C–H bond activation. Journal of Organometallic Chemistry, 845, 135-143. doi:10.1016/j.jorganchem.2017.04.008
Published inJournal of Organometallic Chemistry
DisciplineEpäorgaaninen ja analyyttinen kemia
© 2017 Elsevier Ltd. This is a final draft version of an article whose final and definitive form has been published by Elsevier. Published in this repository with the kind permission of the publisher.
Synthesis, characterization and reaction chemistry of lutetium alkylamido LLu(CH2SiMe3)(NHCPh3) (2), L = 2,5-[Ph2P=N(4-iPrC6H4)]2N(C4H2)–, is reported. Complex 2 undergoes cyclometalation of the NHCPh3 ligand at elevated temperatures to produce the orthometalated complex LLu(κ2−N,C-(NHCPh2(C6H4))) (3) which converts to 0.5 equivalents of bis(amido) LLu(NHCPh3)2 (4) upon heating at 80 °C for 24 h. Reaction of complex 2 with 4-dimethylaminopyridine (DMAP) does not promote alkane elimination nor imido formation. A kinetic analysis of the thermal decomposition of complex 2, supported by deuterium labelling studies and computational analysis (PBE0/def2-TZVP/SDD(Lu)), indicate direct Csp2–H activation, rather than C–H addition across a transient LLu=NCPh3 species, occurs.
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Insights into the decomposition pathway of a lutetium alkylamido complex via intramolecular C–H bond activation Knott, Jackson P.; Hänninen, Mikko M.; Rautiainen, Mikko; Tuononen, Heikki; Hayes, Paul G. (Elsevier B.V., 2017)Synthesis, characterization and reaction chemistry of lutetium alkylamido LLu(CH2SiMe3)(NHCPh3) (2), L = 2,5-[Ph2P=N(4-iPrC6H4)]2N(C4H2)–, is reported. Complex 2 undergoes cyclometalation of the NHCPh3 ligand at elevated ...
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