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Druckeffekte auf organische Reaktionen in Fluiden – eine neue theoretische Perspektive

Journal Article · · Angewandte Chemie
 [1];  [1];  [2]
  1. Department of Chemistry and Chemical Biology, Baker Laboratory Cornell University Ithaca NY 14853-1301 USA
  2. Department of Chemical Science, Life Science and Environmental Sustainability University of Parma Viale Parco Area delle Scienze. 17/a Parma 43100 Italien
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Abstract

Dieser Aufsatz zeigt eine neue Perspektive für die Untersuchung chemischer Reaktionen in komprimierten flüssigen Medien auf. Wir beginnen, indem wir die wesentlichen Einsichten zusammenfassen, die in über 50 Jahren experimenteller Studien an organischen Reaktionen in Lösung unter Druck gewonnen wurden. Diese Arbeiten führten zu einer zuverlässigen Beurteilung der kritischen Rolle der Aktivierungs‐ (Δ ≠ V) und Reaktionsvolumen (ΔV) beim Verständnis von Druckeffekten auf Geschwindigkeiten und Gleichgewichte organischer Reaktionen. Eine kürzlich entwickelte Computermethode, die XP‐PCM‐Methode (XP‐PCM=extreme pressure polarizable continuum model), die quantenchemische Berechnungen von Reaktionswegen von Molekülen unter Druck vornehmen kann, wird eingeführt. Eine Fallstudie der Diels‐Alder‐Cycloaddition von Cyclopentadien mit Ethylen soll – in pädagogischem Detail – der Beschreibung der Methode dienen. Anschließend wenden wir die XP‐PCM‐Methode auf eine Auswahl anderer pericyclischer Reaktionen an, einschließlich der Diels‐Alder‐Cycloaddition von Butadien mit Ethylen, der elektrocyclischen Ringöffnung von Cyclobuten, dem elektrocyclischen Ringschluss von Z‐Hexatrien, der [1,5]‐H‐Verschiebung in Z‐Pentadien und der Cope‐Umlagerung. Diese Reaktionen dienen als Beispiele für einige der häufigsten Kombinationen von Δ ≠ V und ΔV. Interessante Phänomene, wie die Verschiebung eines Übergangszustands entlang der Reaktionskoordinate, ein Wechsel des geschwindigkeitsbestimmenden Schrittes und die mögliche Umwandlung eines Übergangszustands in ein stabiles Minimum, werden durch diese Berechnungen aufgedeckt. Ein Profil des Reaktionsvolumens, entsprechend der Änderung des Volumens des reagierenden Moleküls im Verlauf der Reaktion, erweist sich als nützlich.

Sponsoring Organization:
USDOE
Grant/Contract Number:
SC0001057
OSTI ID:
1377942
Journal Information:
Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 37 Vol. 129; ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

References (106)

The Effect of Pressure on Organic Reactions journal September 2000
Computational Organic Chemistry book January 2007
The Effect of Pressure on Organic Reactions: Basic Principles and Mechanistic Applications book January 2002
Reactions at supercritical conditions: Applications and fundamentals journal July 1995
Die Erhaltung der Orbitalsymmetrie journal November 1969
Hochdruck-kinetische Untersuchungen in der Organischen und Makromolekularen Chemie journal March 1975
Chemie in komprimierten Lösungen journal November 1980
Übergangsstrukturen in pericyclischen Reaktionen von Kohlenwasserstoffen journal June 1992
Der Druckeffekt bei pericyclischen Umlagerungen: Cope-Umlagerung, Elektrocyclisierung und intramolekulare Diels-Alder-Reaktion journal May 1994
Breaking Down Barriers: The Liaison Between Sigmatropic Shifts, Electrocyclic Reactions, and Three-Center Cations journal December 2003
Chemie unter höchsten Drücken: eine Herausforderung für die chemische Intuition journal May 2007
Understanding Covalent Mechanochemistry journal May 2009
Pressure-Induced Polymerization of Acetylene: Structure-Directed Stereoselectivity and a Possible Route to Graphane journal May 2017
The Conservation of Orbital Symmetry journal November 1969
High Pressure Kinetic Investigations in Organic and Macromolecular Chemistry journal March 1975
Chemistry in Compressed Solutions journal November 1980
Transition Structures of Hydrocarbon Pericyclic Reactions journal June 1992
The Pressure Effect in Pericyclic Rearrangements: the Cope Rearrangement, Electrocyclization, and the Intramolecular Diels-Alder Reaction journal June 1994
Breaking Down Barriers: The Liaison Between Sigmatropic Shifts, Electrocyclic Reactions, and Three-Center Cations journal December 2003
The Chemical Imagination at Work inVery Tight Places journal May 2007
Understanding Covalent Mechanochemistry journal May 2009
Pressure-Induced Polymerization of Acetylene: Structure-Directed Stereoselectivity and a Possible Route to Graphane journal May 2017
Mechanochemistry: The Mechanical Activation of Covalent Bonds journal October 2005
Should the Woodward-Hoffmann Rules be Applied to Mechanochemical Reactions? journal February 2015
A new extension of the polarizable continuum model: Toward a quantum chemical description of chemical reactions at extreme high pressure journal October 2015
Recent Advances in Organic Synthesis under High Pressure journal April 1997
Soft Materials and Biomaterials under Pressure book January 2004
Organic Synthesis at High Pressure book January 1987
High Pressure Kinetic Effects as Mechanistic Probes in Organic Chemistry book January 1993
The Future of High Pressure Organic Synthesis book January 1993
Activation of Organic Reactions. High Pressure vs New Emerging Activation Modes book January 1999
Reactions in Supercritical Fluids book January 1994
Kinetics and Selectivity of Chemical Processes in Fluid Phases book January 1994
The influence of polarization functions on molecular orbital hydrogenation energies journal January 1973
Hochdruckversuche—IX journal January 1978
A matrix partitioning approach to the calculation of intermolecular potentials. General theory and some examples journal February 1990
Kinetics of the cope rearrangement of 1,1-dideuteriohexa-1,5-diene journal January 1971
Effect of pressure on the conrotatory opening of cyclobutenes. An unexpected result? journal March 1998
Bacterial survival following shock compression in the GigaPascal range journal September 2017
Correlation between pressure and steric interactions in organic reactions journal April 2005
Diels–Alder Cycloaddition of Cyclopentadiene and C 60 at the Extreme High Pressure journal May 2017
Molecular Origin of Mechanical Sensitivity of the Reaction Rate in Anthracene Cyclophane Isomerization Reveals Structural Motifs for Rational Design of Mechanophores journal August 2016
Systematic Enumeration of sp 3 Nanothreads journal July 2015
The path of chemical reactions - the IRC approach journal December 1981
Polar Attributes of Supercritical Carbon Dioxide journal June 2005
Metadynamics as a Tool for Exploring Free Energy Landscapes of Chemical Reactions journal February 2006
High Pressure Electrides: A Predictive Chemical and Physical Theory journal February 2014
Activation and reaction volumes in solution. 2 journal May 1989
Energy Disposition in Reactive Intermediates journal March 2013
A scaled particle theory of aqueous and nonaqueous solutions journal December 1976
Activation and reaction volumes in solution journal August 1978
Organic Chemical Reactions in Supercritical Water journal February 1999
Activation and Reaction Volumes in Solution. 3 journal September 1998
Quantum Mechanical Continuum Solvation Models journal August 2005
Modeling Molecular Systems at Extreme Pressure by an Extension of the Polarizable Continuum Model (PCM) Based on the Symmetry-Adapted Cluster-Configuration Interaction (SAC–CI) Method: Confined Electronic Excited States of Furan as a Test Case journal April 2015
Reactions in supercritical fluids - a review journal January 1986
Nonequilibrium effects in kinetics of cycloaddition reactions under high pressure journal July 1991
Ice under pressure: transition to symmetrical hydrogen bonds journal October 1983
Improvements of the continuum model. 1. Application to the calculation of the vaporization thermodynamic quantities of nonassociated liquids journal March 1988
van der Waals Volumes and Radii journal March 1964
Torquoselectivity in the electrocyclic conversion of benzocyclobutenes to o-xylylenes journal February 1992
Cooperative and Competitive Substituent Effects on the Cope Rearrangements of Phenyl-Substituted 1,5-Hexadienes Elucidated by Becke3LYP/6-31G* Calculations journal August 2000
The Cope Rearrangement Revisited Again. Results of Ab Initio Calculations beyond the CASSCF Level journal February 1994
Perturbation of the Degenerate, Concerted Cope Rearrangement by Two Phenyl Groups in Active Positions of (E)-1,4-Diphenylhexa-1,5-diene. Acceleration by High Pressure as Criterion of Cyclic Transition States journal May 1994
Transition Regions in the Cope Rearrangement of 1,5-Hexadiene and Its Cyano Derivatives journal August 2000
Stereoselective substituent effects on conrotatory electrocyclic reactions of cyclobutenes journal December 1984
Possible role of 1,4-cyclohexylene intermediates in Cope rearrangements journal January 1973
A Correlation of Reaction Rates journal January 1955
Control Elements in Dynamically Determined Selectivity on a Bifurcating Surface journal November 2008
The Effect of Pressure on Cyclizations. The Ring-Size Dependent Reaction Volumes of the Cyclization of 1-Alkenes to Cycloalkanes. Experimental Measurement of Activation and Reaction Volumes of the Intramolecular Diels−Alder Reaction of 1,3,8-Nonatriene and 1,3,9-Decatriene. Temperature Dependence of Activation and Reaction Volumes journal July 1998
Molecular Dynamics of the Diels–Alder Reactions of Tetrazines with Alkenes and N 2 Extrusions from Adducts journal April 2015
High-Pressure Electrides: The Chemical Nature of Interstitial Quasiatoms journal March 2015
Linearly Polymerized Benzene Arrays As Intermediates, Tracing Pathways to Carbon Nanothreads journal November 2015
Transition Structures of Thermally Allowed Disrotatory Electrocyclizations. The Prediction of Stereoselective Substituent Effects in Six-Electron Pericyclic Reactions journal November 1995
Prediction and experimental verification of the stereoselective electrocyclization of 3-formylcyclobutene journal August 1987
A Standard Set of Pericyclic Reactions of Hydrocarbons for the Benchmarking of Computational Methods:  The Performance of ab Initio, Density Functional, CASSCF, CASPT2, and CBS-QB3 Methods for the Prediction of Activation Barriers, Reaction Energetics, and Transition State Geometries journal December 2003
Vibrational Frequencies of Fullerenes C 60 and C 70 under Pressure Studied with a Quantum Chemical Model Including Spatial Confinement Effects journal June 2014
Self-Consistent-Field Calculation of Pauli Repulsion and Dispersion Contributions to the Solvation Free Energy in the Polarizable Continuum Model journal February 1997
Theoretical Studies of the Electrocyclic Reaction Mechanisms of Hexatriene to Cyclohexadiene journal April 1999
Biasing reaction pathways with mechanical force journal March 2007
Inducing and quantifying forbidden reactivity with single-molecule polymer mechanochemistry journal February 2015
Benzene-derived carbon nanothreads journal September 2014
Solvothermal processes: a route to the stabilization of new materials journal January 1999
Constraining molecules at the closest approach: chemistry at high pressure journal January 2007
Some applications of the transition state method to the calculation of reaction velocities, especially in solution journal January 1935
On the Symmetry of the Hydrogen Bonds in Ice VII journal January 1972
The Activated Complex in Chemical Reactions journal February 1935
A fresh look at dense hydrogen under pressure. II. Chemical and physical models aiding our understanding of evolving H–H separations journal February 2012
A fresh look at dense hydrogen under pressure. III. Two competing effects and the resulting intra-molecular H-H separation in solid hydrogen under pressure journal February 2012
Calculation and analysis of the harmonic vibrational frequencies in molecules at extreme pressure: Methodology and diborane as a test case journal October 2012
Minima hopping guided path search: An efficient method for finding complex chemical reaction pathways journal June 2014
Dynamics, transition states, and timing of bond formation in Diels-Alder reactions journal July 2012
The Compressibility of Media under Extreme Pressures journal September 1944
Enhanced sampling of chemical and biochemical reactions with metadynamics journal June 2014
High pressure and the origin of life journal October 2002
Change of Phase under Pressure. I. The Phase Diagram of Eleven Substances with Especial Reference to The Melting Curve journal March 1914
Density-functional exchange-energy approximation with correct asymptotic behavior journal September 1988
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal January 1988
Charge separation and polymerization of hydrocarbons at an ultrahigh pressure journal July 2004
Ab initio studies on high pressure phases of ice journal July 1992
Cascading Fermi Resonances and the Soft Mode in Dense Ice journal June 1997
Compression of Ice to 210 Gigapascals: Infrared Evidence for a Symmetric Hydrogen-Bonded Phase journal July 1996
Areas, Volumes, Packing, and Protein Structure journal June 1977
The Effect of Pressure on the Diels-Alder Reaction journal September 1974
Glossary of terms used in physical organic chemistry (IUPAC Recommendations 1994) journal January 1994
High-Pressure Biochemistry and Biophysics journal January 2013

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