Energetics and mechanism of organolanthanide-mediated aminoalkene hydroamination/cyclization. A density functional theory analysis

Alessandro Motta, Giuseppe Lanza, Ignazio L. Fragalà, Tobin J Marks

Research output: Contribution to journalArticle

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Abstract

This contribution focuses on organolanthanide-mediated hydroamination processes and analyzes the hydroamination/cyclization of a prototypical aminoalkene, NH2(CH2)3CH=CH2, catalyzed by Cp2LaCH(TMS)2, using density functional theory. The reaction is found to occur in two steps, namely, cyclization to form La-C and C-N bonds, and subsequent La-C protonolysis. Calculations have been carried out for (i) insertion of the olefmic moiety into the La-N bond via a four-center transition state and (ii) protonolysis by a second substrate molecule. The cyclized amine then dissociates, thus restoring the active catalyst. DFT energy profiles have been determined for the turnover-limiting insertion of the 1-amidopent-4-ene C=C double bond into the La-NH- bond. DFT calculations of geometries and the stabilities of reactants, intermediates, and products have been analyzed. The picture that emerges involves concerted, rate-limiting, slightly endothermic insertion of the alkene fragment into the La-N(amido) bond via a highly organized, seven-membered chairlike cyclic transition state (ΔHcalcd = 11.3 kcal/mol, ΔScalcd = -14.6 cal/mol K). The resulting cyclopentylmethyl complex then undergoes exothermic protonolysis to yield an amine-amido complex, the resting state of the catalyst. Thermodynamic and kinetic estimates are in excellent agreement with experimental data.

Original languageEnglish
Pages (from-to)4097-4104
Number of pages8
JournalOrganometallics
Volume23
Issue number17
DOIs
Publication statusPublished - Aug 16 2004

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Cyclization
Discrete Fourier transforms
Amines
Density functional theory
insertion
density functional theory
Catalysts
amines
Alkenes
catalysts
Thermodynamics
alkenes
Molecules
Kinetics
Geometry
Substrates
fragments
thermodynamics
kinetics
estimates

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Energetics and mechanism of organolanthanide-mediated aminoalkene hydroamination/cyclization. A density functional theory analysis. / Motta, Alessandro; Lanza, Giuseppe; Fragalà, Ignazio L.; Marks, Tobin J.

In: Organometallics, Vol. 23, No. 17, 16.08.2004, p. 4097-4104.

Research output: Contribution to journalArticle

Motta, Alessandro ; Lanza, Giuseppe ; Fragalà, Ignazio L. ; Marks, Tobin J. / Energetics and mechanism of organolanthanide-mediated aminoalkene hydroamination/cyclization. A density functional theory analysis. In: Organometallics. 2004 ; Vol. 23, No. 17. pp. 4097-4104.
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