Cyclotrimerization of Acetylene in Gas Phase V+(C2H2)n Complexes: Detection of Intermediates and Products with Infrared Spectroscopy

Marks, Joshua H.; Ward, Timothy B; Brathwaite, Antonio D.; Ferguson, Sojourna; Duncan, Michael A

doi:10.1021/acs.jpca.9b04962

Title: Cyclotrimerization of Acetylene in Gas Phase V⁺(C₂H₂)_n Complexes: Detection of Intermediates and Products with Infrared Spectroscopy

Abstract

Infrared laser spectroscopy and mass spectrometry were used to determine the structures of intermediates and products in the single-atom-catalyzed trimerization of acetylene to form benzene. Complexes of the form V⁺(C₂H₂)_n were produced in the gas phase via laser ablation in a pulsed-nozzle source, size-selected with a mass spectrometer, and studied with infrared laser photodissociation spectroscopy. Density Functional Theory (DFT) calculations were performed in support of the experiments. Single- and doub le-acetylene complexes form V⁺(C₂H₂)_n metallacycle structures. Three-acetylene complexes exhibit a surprising dependence on the acetylene concentration, forming V⁺(C₂H₂)₃and (C₂H₂)V⁺(C₄H₄) tri- and dimetallacycle ion structures at low concentration, and eventually V⁺(benzene) at higher concentrations. Finally, these observations reveal intermediates along the reaction path of acetylene cyclotrimerization to benzene.

Authors:

Marks, Joshua H. ^[1]; Ward, Timothy B ^[1]; Brathwaite, Antonio D. ^[2]; Ferguson, Sojourna ^[3];

^[1]

Univ. of Georgia, Athens, GA (United States)
Emory Univ., Atlanta, GA (United States)
Univ. of the Virgin Islands, St. Thomas (United States)

Publication Date:: Thu Jul 11 00:00:00 EDT 2019

Research Org.:: Univ. of Georgia, Athens, GA (United States). Research Foundation

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); US Air Force Office of Scientific Research (AFOSR); National Science Foundation (NSF)

OSTI Identifier:: 1615627

Grant/Contract Number:: SC0018835; FA9550-15-1-0088

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

Additional Journal Information:: Journal Volume: 123; Journal Issue: 31; Journal ID: ISSN 1089-5639

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; laser spectroscopy; molecular beams; mass spectrometry; infrared spectroscopy

Citation Formats


                    Marks, Joshua H., Ward, Timothy B, Brathwaite, Antonio D., Ferguson, Sojourna, and Duncan, Michael A. Cyclotrimerization of Acetylene in Gas Phase V+(C2H2)n Complexes: Detection of Intermediates and Products with Infrared Spectroscopy.  United States: N. p., 2019. 
Web.  doi:10.1021/acs.jpca.9b04962.

Copy to clipboard


                    Marks, Joshua H., Ward, Timothy B, Brathwaite, Antonio D., Ferguson, Sojourna, & Duncan, Michael A. Cyclotrimerization of Acetylene in Gas Phase V+(C2H2)n Complexes: Detection of Intermediates and Products with Infrared Spectroscopy.  United States.  https://doi.org/10.1021/acs.jpca.9b04962

Copy to clipboard


                    Marks, Joshua H., Ward, Timothy B, Brathwaite, Antonio D., Ferguson, Sojourna, and Duncan, Michael A. Thu .  
"Cyclotrimerization of Acetylene in Gas Phase V+(C2H2)n Complexes: Detection of Intermediates and Products with Infrared Spectroscopy".  United States.  https://doi.org/10.1021/acs.jpca.9b04962.  https://www.osti.gov/servlets/purl/1615627.

Copy to clipboard


                    
@article{osti_1615627,

  title        = {Cyclotrimerization of Acetylene in Gas Phase V+(C2H2)n Complexes: Detection of Intermediates and Products with Infrared Spectroscopy},

  author       = {Marks, Joshua H. and Ward, Timothy B and Brathwaite, Antonio D. and Ferguson, Sojourna and Duncan, Michael A},

  abstractNote = {Infrared laser spectroscopy and mass spectrometry were used to determine the structures of intermediates and products in the single-atom-catalyzed trimerization of acetylene to form benzene. Complexes of the form V+(C2H2)n were produced in the gas phase via laser ablation in a pulsed-nozzle source, size-selected with a mass spectrometer, and studied with infrared laser photodissociation spectroscopy. Density Functional Theory (DFT) calculations were performed in support of the experiments. Single- and doub le-acetylene complexes form V+(C2H2)n metallacycle structures. Three-acetylene complexes exhibit a surprising dependence on the acetylene concentration, forming V+(C2H2)3and (C2H2)V+(C4H4) tri- and dimetallacycle ion structures at low concentration, and eventually V+(benzene) at higher concentrations. Finally, these observations reveal intermediates along the reaction path of acetylene cyclotrimerization to benzene.},

  doi          = {10.1021/acs.jpca.9b04962},

  journal      = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},

  number       = 31,

  volume       = 123,

  place        = {United States},

  year         = {Thu Jul 11 00:00:00 EDT 2019},

  month        = {Thu Jul 11 00:00:00 EDT 2019}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acs.jpca.9b04962

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 15 works

Citation information provided by
Web of Science

Figures / Tables:

Table 1: Relative energies between isomers of V(C₂H₂)_n+ (n = 0–3). These values are zero-point corrected using the scaling factor noted earlier (0.96) to account for anharmonicity.

All figures and tables (12 total)

Save / Share:

Export Metadata

Save to My Library

Figures / Tables found in this record:

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

Similar Records in DOE PAGES and OSTI.GOV collections:

Molecular Heterogeneous Catalysis: a Single-Site Zeolite-Supported Rhodium Complex for Acetylene Cyclotrimerization

Journal Article Kletnieks, P W ; Liang, A J ; Craciun, R ; ... - Chem. Eur. J.13:7294,2007

By anchoring metal complexes to supports, researchers have attempted to combine the high activity and selectivity of molecular homogeneous catalysis with the ease of separation and lack of corrosion of heterogeneous catalysis. However, the intrinsic nonuniformity of supports has limited attempts to make supported catalysts truly uniform. We report the synthesis and performance of such a catalyst, made from [Rh(C{sub 2}H{sub 4}){sub 2}(CH{sub 3}COCHCOCH{sub 3})] and a crystalline support, dealuminated Y zeolite, giving {l_brace}Rh(C{sub 2}H{sub 4}){sub 2}{r_brace} groups anchored by bonds to two zeolite oxygen ions, with the structure determined by extended X-ray absorption fine structure (EXAFS) spectroscopy and themore »« less
Reaction pathways of acetylene on Pd/W(211): A TPD and HREELS investigation

Journal Article Abdelrehim, I M ; Pelhos, K ; Madey, T E ; ... - Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical

In an ongoing investigation to study structure-reactivity relationships on bimetallic surfaces, acetylene cyclotrimerization to form benzene is of particular interest: in this structure-sensitive catalytic reaction, C-C and C-H bonds can be formed readily under ultrahigh vacuum (UHV) conditions without C-C bond breaking. In this paper, the authors present results for acetylene cyclization and hydrogenation on Pd/W(211). Pd on W is chosen because it is a morphologically unstable system, and W(211) facets develop after annealing Pd/W(111) to {ge}700 K. Temperature-programmed desorption (TPD) results exhibit negligible amounts of benzene detected from acetylene adsorption on clean W(211). A single monolayer (ML) of Pdmore »« less
https://doi.org/10.1021/jp982613s
Microsolvation in V⁺(H₂O)_n Clusters Studied with Selected-Ion Infrared Spectroscopy

Journal Article Carnegie, Prosser D. ; Marks, Joshua H. ; Brathwaite, Antonio D. ; ... - Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

Gas phase ion-molecule clusters of the form V⁺(H₂O)_n (n = 1-30) are produced by laser vaporization in a supersonic expansion. These ions are analyzed and mass-selected with a time-of-flight mass spectrometer and investigated with infrared laser photodissociation spectroscopy. The small clusters (n ≤ 7) are studied with argon tagging, while the larger clusters are studied via the elimination of water molecules. The vibrational spectra for the small clusters include only free O-H stretching vibrations, while larger clusters exhibit red-shifted hydrogen bonding vibrations. The spectral patterns reveal that the coordination around V⁺ ions is completed with four water molecules. A symmetricmore »« less
Cited by 10
https://doi.org/10.1021/acs.jpca.9b11275

Full Text Available
Combined Experimental and Computational Investigation of the Elementary Reaction of Ground State Atomic Carbon (C; ³P_j) with Pyridine (C₅H₅N; X¹A₁) via Ring Expansion and Ring Degradation Pathways

Journal Article Lucas, Michael ; Thomas, Aaron M. ; Kaiser, Ralf I. ; ... - Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

In t his work, we explored the elementary reaction of atomic carbon (C; ³P_j) with pyridine (C₅H₅N; X¹A₁) at a collision energy of 34 ± 4 kJ mol-1 utilizing the crossed molecular beams technique. Forwardconvolution fitting of the data was combined with high-level electronic structure calculations and statistical (RRKM) calculations on the triplet C₆H₅N potential energy surface (PES). These investigations reveal that the reaction dynamics are indirect and dominated by large range reactive impact parameters leading via barrier-less addition to the nitrogen atom and to two chemically non-equivalent ‘aromatic’ carbon-carbon bonds forming three distinct collision complexes. At least two reactionmore »« less
Cited by 7
https://doi.org/10.1021/acs.jpca.8b00756

Full Text Available
Pyrolysis of acetylene in sonolytic cavitation bubbles in aqueous solution

Journal Article Hart, E J ; Fischer, C H ; Henglein, A - Journal of Physical Chemistry; (USA)

Water was irradiated with 1 MHz ultrasound (about 2 W/cm{sup 2}) under mixtures of argon and acetylene of various compositions. A few experiments were performed using deuterated acetylene. Acetylene is rapidly consumed, the maximum rate occurring at a solution concentration of C{sub 2}H{sub 2} of 2 {times} 10{sup {minus}3} M. The products are H{sub 2}, CO, CH{sub 4}, a great number of hydrocarbons containing two to about eight C atoms, formic and acetic acids, formaldehyde and acetaldehyde, and insoluble soot. Some larger product molecules are benzene, isomers of benzene, phenylacetylene, styrene, and naphthalene. The products are similar to the onesmore »« less
https://doi.org/10.1021/j100364a047

Similar Records

Title: Cyclotrimerization of Acetylene in Gas Phase V+(C2H2)n Complexes: Detection of Intermediates and Products with Infrared Spectroscopy

Abstract

Citation Formats

Figures / Tables:

Title: Cyclotrimerization of Acetylene in Gas Phase V⁺(C₂H₂)_n Complexes: Detection of Intermediates and Products with Infrared Spectroscopy