Insights into the decomposition pathway of a lutetium alkylamido complex via intramolecular C–H bond activation
Knott, J. P., Hänninen, M. M., Rautiainen, J. M., Tuononen, H. M., & 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. https://doi.org/10.1016/j.jorganchem.2017.04.008
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Journal of Organometallic ChemistryDate
2017Discipline
Epäorgaaninen ja analyyttinen kemiaFysikaalinen kemiaNanoscience CenterInorganic and Analytical ChemistryPhysical ChemistryNanoscience CenterCopyright
© 2017 Elsevier B.V. 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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Research Council of FinlandFunding program(s)
Academy Project, AoF; Postdoctoral Researcher, AoFAdditional information about funding
This research was generously supported by the Natural Sciences and Engineering Research Council (NSERC) of Canada (341687), the Canada Foundation for Innovation (CFI), the Academy of Finland (282499 and 274505) and the University of Jyväskylä. We are grateful to the Finnish CSC-IT Center for Science for allocation of computational resources. Mr. Tony Montina is acknowledged for expert technical a ...
