Tetrahedrane — Dossier of an Unknown

Nemirowski, Adelina; Reisenauer, Hans Peter

doi:10.1002/chin.200651053

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“…Additionally, chlorine atoms in the structure of key species appears to stabilize biradicals and carbenes formed in the nonradical channels, 38−40 lowering the barriers of important steps relative to those found on a nonchlorinated PES. 84,106,107 Consequently, we anticipate that as the degree of chlorination decreases, the importance of nonradical channels is likely to diminish, playing a negligible role (chemistry now favors radical-carried processes) once nonchlorinated species are explored.…”

Section: ■ Discussion and Conclusionmentioning

confidence: 99%

Experimental and Theoretical Studies into the Formation of C₄–C₆ Products in Partially Chlorinated Hydrocarbon Pyrolysis Systems: A Probabilistic Approach to Congener-Specific Yield Predictions

McIntosh

Russell

2014

J. Phys. Chem. A

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This work presents a study of the pyrolytic formation of vinylacetylene and benzene congeners formed from chlorinated hydrocarbon precursors, a complex, multipath polymerization system formed in a monomer-rich environment. (Co-)pyrolyses of dichloro- and trichloroethylene yield a rich array of products, and assuming a single dominant underlying growth mechanism, this (on comparing expected and observed products) allows a number of potentially competing channels to C4 and C6 products to be ruled out. Poor congener/isomer descriptions rule out even-carbon radical routes, and the absence of C3 and C5 products rule out odd-carbon processes. Vinylidenes appear unable to describe the increased reactivity of acetylenes with chlorination noted in our experiments, leaving molecular acetylene dimerization processes and, in C6 systems, the closely related Diels-Alder cyclization as the likely reaction mechanism. The feasibility of these routes is further supported by ab initio calculations. However, some of the most persuasive evidence is provided by congener-specific yield predictions enabled by the construction of a probability tree analogue of kinetic modeling. This approach is relatively quick to construct, provides surprisingly accurate predictions, and may be a very useful tool in screening for important reaction channels in poorly understood congener- or isomer-rich reaction systems.

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Section: ■ Discussion and Conclusionmentioning

confidence: 99%

Experimental and Theoretical Studies into the Formation of C₄–C₆ Products in Partially Chlorinated Hydrocarbon Pyrolysis Systems: A Probabilistic Approach to Congener-Specific Yield Predictions

McIntosh

Russell

2014

J. Phys. Chem. A

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Tetrahedrane — Dossier of an Unknown

Abstract: 2006 Bridged compounds Q 0060 Tetrahedrane -Dossier of an Unknown -(NEMIROWSKI, A.; REISENAUER, H. P.; SCHREINER*, P. R.; Chem. Eur. J. 12 (2006) 28, 7411-7420; Inst. Org. Chem., Justus-Liebig-Univ., D-35392 Giessen, Germany; Eng.) -Lindner 51-053

Cited by 1 publication

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Experimental and Theoretical Studies into the Formation of C₄–C₆ Products in Partially Chlorinated Hydrocarbon Pyrolysis Systems: A Probabilistic Approach to Congener-Specific Yield Predictions

Experimental and Theoretical Studies into the Formation of C₄–C₆ Products in Partially Chlorinated Hydrocarbon Pyrolysis Systems: A Probabilistic Approach to Congener-Specific Yield Predictions

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Tetrahedrane — Dossier of an Unknown

Abstract: 2006 Bridged compounds Q 0060 Tetrahedrane -Dossier of an Unknown -(NEMIROWSKI, A.; REISENAUER, H. P.; SCHREINER*, P. R.; Chem. Eur. J. 12 (2006) 28, 7411-7420; Inst. Org. Chem., Justus-Liebig-Univ., D-35392 Giessen, Germany; Eng.) -Lindner 51-053

Cited by 1 publication

References 1 publication

Experimental and Theoretical Studies into the Formation of C4–C6 Products in Partially Chlorinated Hydrocarbon Pyrolysis Systems: A Probabilistic Approach to Congener-Specific Yield Predictions

Experimental and Theoretical Studies into the Formation of C4–C6 Products in Partially Chlorinated Hydrocarbon Pyrolysis Systems: A Probabilistic Approach to Congener-Specific Yield Predictions

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Experimental and Theoretical Studies into the Formation of C₄–C₆ Products in Partially Chlorinated Hydrocarbon Pyrolysis Systems: A Probabilistic Approach to Congener-Specific Yield Predictions

Experimental and Theoretical Studies into the Formation of C₄–C₆ Products in Partially Chlorinated Hydrocarbon Pyrolysis Systems: A Probabilistic Approach to Congener-Specific Yield Predictions