Sterically Induced Ligand Framework Distortion Effects on Catalytic Cyclic Ester Polymerizations

Joahanna A. Macaranas, Anna M. Luke, Mukunda Mandal, Benjamin D. Neisen, Daniel J. Marell, Chris Cramer, William B. Tolman

Research output: Contribution to journalArticle

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Abstract

Aluminum alkoxide complexes supported by salen ligands [salen = N,N′-bis(salicylaldimine)-2-methylpropane-1,2-diamine or N,N′-bis(salicylaldimine)-2,2-dimethylpropane-1,3-diamine] with o-adamantyl substituents have been synthesized and investigated for the polymerization of ϵ-caprolactone. Geometric analysis of the catalysts used for the reaction reveals the metal coordination geometries to be intermediate between square-pyramidal and trigonal-bipyramidal. A detailed kinetic study accompanied by density functional theory modeling of key mechanistic steps of the reaction suggest that, in addition to the length of the backbone linker, the o-aryl substituents have a significant impact on the catalyst's reactivity. Bulky ortho substituents favorably distort the precatalyst geometry and thereby foster the achievement of the rate-limiting transition-state geometry at low energetic cost, thus accelerating the reaction.

Original languageEnglish (US)
Pages (from-to)3451-3457
Number of pages7
JournalInorganic Chemistry
Volume57
Issue number6
DOIs
StatePublished - Mar 19 2018

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esters
Esters
Diamines
polymerization
Polymerization
diamines
Ligands
ligands
Geometry
geometry
catalysts
Catalysts
alkoxides
Aluminum
Density functional theory
reactivity
Metals
density functional theory
costs
aluminum

PubMed: MeSH publication types

  • Journal Article

Cite this

Macaranas, J. A., Luke, A. M., Mandal, M., Neisen, B. D., Marell, D. J., Cramer, C., & Tolman, W. B. (2018). Sterically Induced Ligand Framework Distortion Effects on Catalytic Cyclic Ester Polymerizations. Inorganic Chemistry, 57(6), 3451-3457. https://doi.org/10.1021/acs.inorgchem.8b00250

Sterically Induced Ligand Framework Distortion Effects on Catalytic Cyclic Ester Polymerizations. / Macaranas, Joahanna A.; Luke, Anna M.; Mandal, Mukunda; Neisen, Benjamin D.; Marell, Daniel J.; Cramer, Chris; Tolman, William B.

In: Inorganic Chemistry, Vol. 57, No. 6, 19.03.2018, p. 3451-3457.

Research output: Contribution to journalArticle

Macaranas, JA, Luke, AM, Mandal, M, Neisen, BD, Marell, DJ, Cramer, C & Tolman, WB 2018, 'Sterically Induced Ligand Framework Distortion Effects on Catalytic Cyclic Ester Polymerizations', Inorganic Chemistry, vol. 57, no. 6, pp. 3451-3457. https://doi.org/10.1021/acs.inorgchem.8b00250
Macaranas, Joahanna A. ; Luke, Anna M. ; Mandal, Mukunda ; Neisen, Benjamin D. ; Marell, Daniel J. ; Cramer, Chris ; Tolman, William B. / Sterically Induced Ligand Framework Distortion Effects on Catalytic Cyclic Ester Polymerizations. In: Inorganic Chemistry. 2018 ; Vol. 57, No. 6. pp. 3451-3457.
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