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Gas-Phase Synthesis of Boronylallene (H2CCCH(BO)) under Single Collision Conditions: A Crossed Molecular Beams and Computational Study.
J Phys Chem A. 2014 May 29; 118(21):3810-3819.JP

Abstract

The gas phase reaction between the boron monoxide radical (11BO; X2Σ+) and allene (H2CCCH2; X1A1) was investigated experimentally under single collision conditions using the crossed molecular beam technique and theoretically exploiting ab initio electronic structure and statistical (RRKM) calculations. The reaction was found to follow indirect (complex forming) scattering dynamics and proceeded via the formation of a van der Waals complex (11BOC3H4). This complex isomerized via addition of the boron monoxide radical (11BO; X2Σ+) with the radical center located at the boron atom to the terminal carbon atom of the allene molecule forming a H2CCCH211BO intermediate on the doublet surface. The chemically activated H2CCCH211BO intermediate underwent unimolecular decomposition via atomic hydrogen elimination from the terminal carbon atom holding the boronyl group through a tight exit transition state to synthesize the boronylallene product (H2CCCH11BO) in a slightly exoergic reaction (55 ± 11 kJ mol-1). Statistical (RRKM) calculations suggest that minor reaction channels lead to the products 3-propynyloxoborane (CH2(11BO)CCH) and 1-propynyloxoborane (CH3CC11BO) with fractions of 1.5% and 0.2%, respectively. The title reaction was also compared with the cyano (CN; X2Σ+)-allene and boronyl-methylacetylene reactions to probe similarities, but also differences of these isoelectronic systems. Our investigation presents a novel gas phase synthesis and characterization of a hitherto elusive organyloxoborane (RBO) monomer-boronylallene-which is inherently tricky to isolate in the condensed phase except in matrix studies; our work further demonstrates that the crossed molecular beams approach presents a useful tool in investigating the chemistry and synthesis of highly reactive organyloxoboranes.

Authors+Show Affiliations

Department of Chemistry, University of Hawaii at Manoa , Honolulu, Hawaii 96822, United States.Department of Chemistry, University of Hawaii at Manoa , Honolulu, Hawaii 96822, United States.Department of Chemistry, University of Hawaii at Manoa , Honolulu, Hawaii 96822, United States.Quantum Theory Project, University of Florida , Gainesville, Florida 32611, United States.Quantum Theory Project, University of Florida , Gainesville, Florida 32611, United States.Quantum Theory Project, University of Florida , Gainesville, Florida 32611, United States.Quantum Theory Project, University of Florida , Gainesville, Florida 32611, United States.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

24806514

Citation

Maity, Surajit, et al. "Gas-Phase Synthesis of Boronylallene (H2CCCH(BO)) Under Single Collision Conditions: a Crossed Molecular Beams and Computational Study." The Journal of Physical Chemistry. A, vol. 118, no. 21, 2014, pp. 3810-3819.
Maity S, Parker DSN, Kaiser RI, et al. Gas-Phase Synthesis of Boronylallene (H2CCCH(BO)) under Single Collision Conditions: A Crossed Molecular Beams and Computational Study. J Phys Chem A. 2014;118(21):3810-3819.
Maity, S., Parker, D. S. N., Kaiser, R. I., Ganoe, B., Fau, S., Perera, A., & Bartlett, R. J. (2014). Gas-Phase Synthesis of Boronylallene (H2CCCH(BO)) under Single Collision Conditions: A Crossed Molecular Beams and Computational Study. The Journal of Physical Chemistry. A, 118(21), 3810-3819. https://doi.org/10.1021/jp501595n
Maity S, et al. Gas-Phase Synthesis of Boronylallene (H2CCCH(BO)) Under Single Collision Conditions: a Crossed Molecular Beams and Computational Study. J Phys Chem A. 2014 May 29;118(21):3810-3819. PubMed PMID: 24806514.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Gas-Phase Synthesis of Boronylallene (H2CCCH(BO)) under Single Collision Conditions: A Crossed Molecular Beams and Computational Study. AU - Maity,Surajit, AU - Parker,Dorian S N, AU - Kaiser,Ralf I, AU - Ganoe,Brad, AU - Fau,Stefan, AU - Perera,Ajith, AU - Bartlett,Rodney J, Y1 - 2014/05/15/ PY - 2014/5/9/pubmed PY - 2014/5/9/medline PY - 2014/5/9/entrez SP - 3810 EP - 3819 JF - The journal of physical chemistry. A JO - J Phys Chem A VL - 118 IS - 21 N2 - The gas phase reaction between the boron monoxide radical (11BO; X2Σ+) and allene (H2CCCH2; X1A1) was investigated experimentally under single collision conditions using the crossed molecular beam technique and theoretically exploiting ab initio electronic structure and statistical (RRKM) calculations. The reaction was found to follow indirect (complex forming) scattering dynamics and proceeded via the formation of a van der Waals complex (11BOC3H4). This complex isomerized via addition of the boron monoxide radical (11BO; X2Σ+) with the radical center located at the boron atom to the terminal carbon atom of the allene molecule forming a H2CCCH211BO intermediate on the doublet surface. The chemically activated H2CCCH211BO intermediate underwent unimolecular decomposition via atomic hydrogen elimination from the terminal carbon atom holding the boronyl group through a tight exit transition state to synthesize the boronylallene product (H2CCCH11BO) in a slightly exoergic reaction (55 ± 11 kJ mol-1). Statistical (RRKM) calculations suggest that minor reaction channels lead to the products 3-propynyloxoborane (CH2(11BO)CCH) and 1-propynyloxoborane (CH3CC11BO) with fractions of 1.5% and 0.2%, respectively. The title reaction was also compared with the cyano (CN; X2Σ+)-allene and boronyl-methylacetylene reactions to probe similarities, but also differences of these isoelectronic systems. Our investigation presents a novel gas phase synthesis and characterization of a hitherto elusive organyloxoborane (RBO) monomer-boronylallene-which is inherently tricky to isolate in the condensed phase except in matrix studies; our work further demonstrates that the crossed molecular beams approach presents a useful tool in investigating the chemistry and synthesis of highly reactive organyloxoboranes. SN - 1520-5215 UR - https://www.unboundmedicine.com/medline/citation/24806514/Gas_Phase_Synthesis_of_Boronylallene__H2CCCH_BO___under_Single_Collision_Conditions:_A_Crossed_Molecular_Beams_and_Computational_Study_ L2 - https://dx.doi.org/10.1021/jp501595n DB - PRIME DP - Unbound Medicine ER -
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