Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Gas-Phase Synthesis of the Elusive Cyclooctatetraenyl Radical (C 8H7) via Triplet Aromatic Cyclooctatetraene (C8H8) and Non-Aromatic Cyclooctatriene (C8H8) Intermediates

Journal Article · · Angewandte Chemie (International Edition)
 [1];  [2];  [2];  [2];  [3];  [4]
  1. Univ. of Hawaii at Manoa, Honolulu, HI (United States); University of Hawaii at Manoa
  2. Univ. of Hawaii at Manoa, Honolulu, HI (United States)
  3. Dongguk Univ., Seoul (Korea, Republic of)
  4. Florida International Univ., Miami, FL (United States); Samara National Research Univ. (Russia)
+ Show Author Affiliations
The 1,2,4,7-cyclooctatetraenyl radical (C8H7) has been synthesized for the very first time via the bimolecular gas-phase reaction of ground-state carbon atoms with 1,3,5-cycloheptatriene (C7H8) on the triplet surface under single-collision conditions. The barrierless route to the cyclic 1,2,4,7-cyclooctatetraenyl radical accesses exotic reaction intermediates on the triplet surface, which cannot be synthesized via classical organic chemistry methods: the triplet non-aromatic 2,4,6-cyclooctatriene (C8H8) and the triplet aromatic 1,3,5,7-cyclooctatetraene (C8H8). In this study, our approach provides a clean gas-phase synthesis of this hitherto elusive cyclic radical species 1,2,4,7-cyclooctatetraenyl via a single-collision event and opens up a versatile, unconventional path to access this previously largely obscure class of cyclooctatetraenyl radicals, which have been impossible to access through classical synthetic methods.
Research Organization:
Univ. of Hawaii, Honolulu, HI (United States)
Sponsoring Organization:
Ministry of Education and Science of the Russian Federation; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
FG02-03ER15411; FG02-04ER15570
OSTI ID:
1602965
Alternate ID(s):
OSTI ID: 1537449
OSTI ID: 1394005
Journal Information:
Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 44 Vol. 56; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

References (34)

Konsequenzen der Triplett-Aromatizität in 4nπ-Elektronen-Annulenen – die Berechnung magnetischer Abschirmungen für offenkettige Moleküle journal July 1998
Consequences of Triplet Aromaticity in 4nπ-Electron Annulenes: Calculation of Magnetic Shieldings for Open-Shell Species journal August 1998
Über Cyclo-octatetraen journal July 1911
Zur metall-ring-bindung in sandwich-komplexen journal January 1963
Quantentheoretische Beitr�ge zum Benzolproblem: I. Die Elektronenkonfiguration des Benzols und verwandter Verbindungen journal March 1931
Kinetic and thermodynamic issues in the formation of aromatic compounds in flames of aliphatic fuels journal October 1992
Shock tube studies of gas phase reactions preceding the soot formation process journal January 1991
Crossed beam reaction of the phenyl radical, (C6H5, X2A′) with molecular oxygen (O2,X3Σg-): Observation of the phenoxy radical, (C6H5O, X2A′) journal November 2007
A crossed beam investigation of the reactions of tricarbon molecules, C3(X1Σg+), with acetylene, C2H2(X1Σg+), ethylene, C2H4(X1Ag), and benzene, C6H6(X1A1g) journal November 2007
Theoretical study of the reaction mechanism of ethynyl radical with benzene and related reactions on the C8H7 potential energy surface journal June 2008
Theoretical analysis of the transition-state spectrum of the cyclooctatetraene unimolecular reaction: Three degree-of-freedom model calculations journal August 2015
Oxidation of the para -Tolyl Radical by Molecular Oxygen under Single-Collison Conditions: Formation of the para -Toloxy Radical journal November 2016
Free Cyclooctatetraene Dianion: Planarity, Aromaticity, and Theoretical Challenges journal September 2013
Theoretical Studies of An II 2 (C 8 H 8 ) 2 (An = Th, Pa, U, and Np) Complexes: The Search for Double-Stuffed Actinide Metallocenes journal July 2010
Bis(cyclooctatetraenyl)uranium (uranocene). A new class of sandwich complexes that utilize atomic f orbitals journal December 1968
Reaction of Phenyl Radicals with Acetylene:  Quantum Chemical Investigation of the Mechanism and Master Equation Analysis of the Kinetics journal September 2003
Selective Dilithiation of [Ti(η 5 -C 5 H 5 )(η 8 -C 8 H 8 )] and Subsequent Conversion into Neutral and Cationic ansa -Complexes journal April 2011
Structures, Energetics, and Chemical Reactions of Anions Derived from Cyclooctatetraene journal May 1998
The Recombination of Propargyl Radicals and Other Reactions on a C 6 H 6 Potential journal October 2003
Ab Initio Study of the Cyclooctatetraenyl Radical journal April 2005
Bonding Nature and Electron Delocalization of An(COT) 2 , An = Th, Pa, U
  • Páez-Hernández, Dayán; Murillo-López, Juliana A.; Arratia-Pérez, Ramiro
  • The Journal of Physical Chemistry A, Vol. 115, Issue 32 https://doi.org/10.1021/jp203832m
journal August 2011
Toward the Oxidation of the Phenyl Radical and Prevention of PAH Formation in Combustion Systems journal November 2014
Aromaticity and Antiaromaticity in the Low-Lying Electronic States of Cyclooctatetraene journal December 2008
Ligand-Based Reduction and Electron-Transfer-Induced Tub-to-Chair Isomerization of Cyclooctatetraene Ligand in Rh(η 5 -C 5 Ph 5 )(η 4 -C 8 H 8 ) journal April 2004
Uranocene. The First Member of a New Class of Organometallic Derivatives of the f Elements journal July 2004
Structural Diversity in Cyanido Thorocene Complexes journal April 2014
Bending of “Uranocene” ((η 8 -C 8 H 8 ) 2 U): Synthesis and Crystal Structure of the Cyanido Complex [(η 8 -C 8 H 8 ) 2 U(CN)][NEt 4 ] journal April 2008
Anti-Bimetallic Complexes of Divalent Lanthanides with Silylated Pentalene and Cyclooctatetraenyl Bridging Ligands as Molecular Models for Lanthanide-Based Polymers journal October 2009
f-Orbital covalency in the actinocenes (An = Th–Cm): multiconfigurational studies and topological analysis journal January 2014
New evidence for 5f covalency in actinocenes determined from carbon K-edge XAS and electronic structure theory journal January 2014
Exploiting single-ion anisotropy in the design of f-element single-molecule magnets journal January 2011
The reaction of benzene with a ground state carbon atom, C(3Pj) journal September 2000
Formation of resonantly stabilised free radicals via the reactions of atomic carbon, dicarbon, and tricarbon with unsaturated hydrocarbons: theory and crossed molecular beams experiments journal October 2015
Transition-State Spectroscopy of Cyclooctatetraene journal June 1996

Similar Records

Gas‐Phase Synthesis of the Elusive Cyclooctatetraenyl Radical (C 8 H 7 ) via Triplet Aromatic Cyclooctatetraene (C 8 H 8 ) and Non‐Aromatic Cyclooctatriene (C 8 H 8 ) Intermediates
Journal Article · Thu Sep 21 20:00:00 EDT 2017 · Angewandte Chemie · OSTI ID:1394000
Gas-Phase Formation of 1,3,5,7-Cyclooctatetraene (C8H8) through Ring Expansion via the Aromatic 1,3,5-Cyclooctatrien-7-yl Radical (C8H9•) Transient
Journal Article · Wed Nov 30 19:00:00 EST 2022 · Journal of the American Chemical Society · OSTI ID:1914316
Simple, inexpensive synthesis of dipotassium cyclooctatetraenide, K/sub 2/C/sub 8/H/sub 8/
Journal Article · Wed Dec 31 23:00:00 EST 1980 · J. Org. Chem.; (United States) · OSTI ID:6139235

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
gas-phase chemistry
mass spectrometry
reaction dynamics
reaction intermediates
single-collision conditions