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RESEARCH PRODUCT
Insights into the decomposition pathway of a lutetium alkylamido complex via intramolecular C–H bond activation
Mikko M. HänninenMikko M. HänninenHeikki M. TuononenJackson P. KnottPaul G. HayesJ. Mikko Rautiainensubject
Alkanechemistry.chemical_classificationC h bond010405 organic chemistryLigandStereochemistryOrganic ChemistryThermal decompositionchemistry.chemical_element010402 general chemistry01 natural sciencesBiochemistryLutetium3. Good health0104 chemical scienceslutetiumInorganic ChemistryDecomposition pathwaychemistryDeuteriumIntramolecular forceMaterials Chemistrycoordination complexesPhysical and Theoretical Chemistryta116description
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.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2017-09-01 | Journal of Organometallic Chemistry |