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@ARTICLE{Gertig:904185,
      author       = {Gertig, Christoph and Erdkamp, Eric and Ernst, Andreas and
                      Hemprich, Carl and Kröger, Leif C. and Langanke, Jens and
                      Bardow, André and Leonhard, Kai},
      title        = {{R}eaction {M}echanisms and {R}ate {C}onstants of
                      {A}uto‐{C}atalytic {U}rethane {F}ormation and {C}leavage
                      {R}eactions},
      journal      = {ChemistryOpen},
      volume       = {10},
      number       = {5},
      issn         = {2191-1355},
      address      = {Weinheim},
      publisher    = {Wiley-VCH-Verl.},
      reportid     = {FZJ-2021-05755},
      pages        = {534 - 544},
      year         = {2021},
      abstract     = {The chemistry of urethanes plays a key role in important
                      industrial processes. Although catalysts are often used, the
                      study of the reactions without added catalysts provides the
                      basis for a deeper understanding. For the non-catalytic
                      urethane formation and cleavage reactions, the dominating
                      reaction mechanism has long been debated. To our knowledge,
                      the reaction kinetics have not been predicted quantitatively
                      so far. Therefore, we report a new computational study of
                      urethane formation and cleavage reactions. To analyze
                      various potential reaction mechanisms and to predict the
                      reaction rate constants quantum chemistry and transition
                      state theory were employed. For validation, experimental
                      data from literature and from own experiments were used.
                      Quantitative agreement of experiments and predictions could
                      be demonstrated. The calculations confirm earlier
                      assumptions that urethane formation reactions proceed via
                      mechanisms where alcohol molecules act as auto-catalysts.
                      Our results show that it is essential to consider several
                      transition states corresponding to different reaction orders
                      to enable agreement with experimental observations. Urethane
                      cleavage seems to be catalyzed by an isourethane, leading to
                      an observed 2nd-order dependence of the reaction rate on the
                      urethane concentration. The results of our study support a
                      deeper understanding of the reactions as well as a better
                      description of reaction kinetics and will therefore help in
                      catalyst development and process optimization.},
      cin          = {IEK-10},
      ddc          = {540},
      cid          = {I:(DE-Juel1)IEK-10-20170217},
      pnm          = {899 - ohne Topic (POF4-899)},
      pid          = {G:(DE-HGF)POF4-899},
      typ          = {PUB:(DE-HGF)16},
      pubmed       = {pmid:33656808},
      UT           = {WOS:000624635500001},
      doi          = {10.1002/open.202000150},
      url          = {https://juser.fz-juelich.de/record/904185},
}