A1 Journal article (refereed)
Insights into the decomposition pathway of a lutetium alkylamido complex via intramolecular C–H bond activation (2017)

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

JYU authors or editors

Hänninen, Mikko M.
Rautiainen, Mikko
Tuononen, Heikki

Publication details

All authors or editors: Knott, Jackson P.; Hänninen, Mikko M.; Rautiainen, J. Mikko; Tuononen, Heikki M.; Hayes, Paul G.

Journal or series: Journal of Organometallic Chemistry

ISSN: 0022-328X

eISSN: 1872-8561

Publication year: 2017

Volume: 845

Issue number: 0

Pages range: 135-143

Publisher: Elsevier B.V.

Publication country: Netherlands

Publication language: English

DOI: https://doi.org/10.1016/j.jorganchem.2017.04.008

Publication open access: Not open

Publication channel open access:

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/55059

Abstract

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.

Keywords: coordination complexes

Free keywords: lutetium

Fields of science: