Benyzl Alcohol Dehydrogenative Coupling Catalyzed by Defined Mn and Re PNP Pincer Complexes – A Computational Mechanistic Study

Zhihong Wei, Adiran de Aguirre, Kathrin Junge, Matthias Beller, Haijun Jiao

Research output: Contribution to journalArticlepeer-review

18 Scopus citations

Abstract

Density functional theory computations have been carried out to investigate the base free acceptor-less dehydrogenative coupling of benzyl alcohol to benzyl benzoate catalyzed by defined Mn and Re PNP pincer amido M(CO)2(PNP) and amino HM(CO)2(PNHP) complexes [M = Mn, Re; PNP = N{CH2CH2P(isopropyl)2}2]. Benchmark calculations show that B3PW91 have the best and closest agreement with the experiments than DLPNO-CCSD(T). Within all proposed elementary steps, the non-innocent outer-sphere mechanism incorporating the amido complex and the N–H bond is more kinetically favored than the innocent outer-sphere mechanism without the amido complex as well as the inner-sphere mechanism via the de-coordination of one phosphine ligand to create a vacant site for β-hydride elimination. The dehydrogenation of hemiacetal to ester represents the rate-determining step. Both Mn and Re-based catalysts have close free energy barriers and similar catalytic activity. However, the computed apparent barrier is overestimated on the basis of the experimentally determined TOF for the Mn-based complexes.

Original languageEnglish
Pages (from-to)4643-4657
Number of pages15
JournalEuropean Journal of Inorganic Chemistry
Volume2018
Issue number42
DOIs
StatePublished - 15 Nov 2018
Externally publishedYes

Keywords

  • Alcohol dehydrogenative coupling
  • Density functional calculations
  • Manganese
  • Outer-sphere mechanism
  • Pincer complexes
  • Rhenium

Fingerprint

Dive into the research topics of 'Benyzl Alcohol Dehydrogenative Coupling Catalyzed by Defined Mn and Re PNP Pincer Complexes – A Computational Mechanistic Study'. Together they form a unique fingerprint.

Cite this