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The activity of indenylidene derivatives in olefin metathesis catalysts

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Abstract
The first turnover event of an olefin metathesis reaction using a new family of homogenous Ru-based catalysts bearing modified indenylidene ligands has been investigated, using methoxyethylene as a substrate. The study is carried out by means of density functional theory (DFT). The indenylidene ligands are decorated with ortho-methyl and isopropyl groups at both ortho positions of their phenyl ring. DFT results highlight the more sterically demanding indenylidenes have to undergo a more exothermic first phosphine dissociation step. Overall, the study emphasises advantages of increased steric hindrance in promoting the phosphine release, and the relative stability of the corresponding metallacycle over classical ylidene ligands. Mayer bond orders and steric maps provide structural reasons for these effects, whereas NICS aromaticity and conceptual DFT confirm that the electronic parameters do not play a significant role.
Keywords
activation, IMes, indenylidene, olefin metathesis, SIMes, INDEPENDENT CHEMICAL-SHIFTS, GAUSSIAN-BASIS SETS, RU-BASED CATALYSTS, ACTIVATION MECHANISM, BOND ORDER, ATOMS LI, RUTHENIUM, COMPLEXES, ENERGY, PSEUDOPOTENTIALS

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MLA
Voccia, Maria et al. “The Activity of Indenylidene Derivatives in Olefin Metathesis Catalysts.” BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY 14 (2018): 2956–2963. Print.
APA
Voccia, M., Nolan, S., Cavallo, L., & Poater, A. (2018). The activity of indenylidene derivatives in olefin metathesis catalysts. BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY, 14, 2956–2963.
Chicago author-date
Voccia, Maria, Steven Nolan, Luigi Cavallo, and Albert Poater. 2018. “The Activity of Indenylidene Derivatives in Olefin Metathesis Catalysts.” Beilstein Journal of Organic Chemistry 14: 2956–2963.
Chicago author-date (all authors)
Voccia, Maria, Steven Nolan, Luigi Cavallo, and Albert Poater. 2018. “The Activity of Indenylidene Derivatives in Olefin Metathesis Catalysts.” Beilstein Journal of Organic Chemistry 14: 2956–2963.
Vancouver
1.
Voccia M, Nolan S, Cavallo L, Poater A. The activity of indenylidene derivatives in olefin metathesis catalysts. BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY. 2018;14:2956–63.
IEEE
[1]
M. Voccia, S. Nolan, L. Cavallo, and A. Poater, “The activity of indenylidene derivatives in olefin metathesis catalysts,” BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY, vol. 14, pp. 2956–2963, 2018.
@article{8602779,
  abstract     = {The first turnover event of an olefin metathesis reaction using a new family of homogenous Ru-based catalysts bearing modified indenylidene ligands has been investigated, using methoxyethylene as a substrate. The study is carried out by means of density functional theory (DFT). The indenylidene ligands are decorated with ortho-methyl and isopropyl groups at both ortho positions of their phenyl ring. DFT results highlight the more sterically demanding indenylidenes have to undergo a more exothermic first phosphine dissociation step. Overall, the study emphasises advantages of increased steric hindrance in promoting the phosphine release, and the relative stability of the corresponding metallacycle over classical ylidene ligands. Mayer bond orders and steric maps provide structural reasons for these effects, whereas NICS aromaticity and conceptual DFT confirm that the electronic parameters do not play a significant role.},
  author       = {Voccia, Maria and Nolan, Steven and Cavallo, Luigi and Poater, Albert},
  issn         = {1860-5397},
  journal      = {BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY},
  keywords     = {activation,IMes,indenylidene,olefin metathesis,SIMes,INDEPENDENT CHEMICAL-SHIFTS,GAUSSIAN-BASIS SETS,RU-BASED CATALYSTS,ACTIVATION MECHANISM,BOND ORDER,ATOMS LI,RUTHENIUM,COMPLEXES,ENERGY,PSEUDOPOTENTIALS},
  language     = {eng},
  pages        = {2956--2963},
  title        = {The activity of indenylidene derivatives in olefin metathesis catalysts},
  url          = {http://dx.doi.org/10.3762/bjoc.14.275},
  volume       = {14},
  year         = {2018},
}

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