Matrix Isolation of Aryl(trifluoromethyl)carbenes, Heteroaryl(trifluoromethyl)carbenes and Phenylbis(trifluoromethyl)carbenes
type: CreativeWork
description: We have isolated and studied 2-naphthyl(trifluoromethyl)carbene, 1-naphthyl(trifluoromethyl)carbene, 4-pyridyl (trifluoromethyl)carbene, 2-pyridyl(trifluoromethyl)carbene, 3-pyridyl (trifluoromethyl)carbene, 3-bromo-5-pyridyl(trifluoromethyl)carbene, meta-phenylbis(trifluoromethyl)carbene and paraphenylbis(trifluoromethyl)carbene in low temperature matrices for the first time. Thenaphthyl(trifluoromethyl)carbenes are photostable and have triplet ground states in matrices asmost of the other studied ary(trifluoromethyl)carbenes. The 1- and 2-naphthyl(trifluoromethyl)diazirines, the precursors of 1- and 2-naphthyl(trifluoromethyl)carbenes, have dissimilar geometric structures leading to differentUV/Vis absorptions. In the studied pyridyl(trifluoromethyl)carbenes, 4-pyridyl(trifluoromethyl)carbene was the most stable one in matrice: no photoproduct from 4-pyridyl(trifluoromethyl)carbene was observed. However, we obtained a small amount ofphotoproducts of 2 - pyridyl(trifluoromethyl)carbene, even though the result was not repeatable.The most reactive isomer was 3 - pyridyl(trifluoromethyl)carbene, which could decompose underprolonged irradiation. The derivative of 3 - pyridyl(trifluoromethyl)carbene, 3 - bromo - 5 -pyridyl(trifluoromethyl)carbene, was more photolabile and could be converted to otherintermediates with comparatively short term irradiation. All the studied pyridylcarbenes havetriplet ground states. Although they were photostable, phenyl(trifluoromethyl)biscarbenesattracted our attention due to their interesting electronic structures. meta-Phenyl(trifluoromethyl)carbene has a quintet ground state, while the overall multiplicity of para- phenyl(trifluoromethyl)carbene is a singlet with a diradical structure.
abstract: We have isolated and studied 2-naphthyl(trifluoromethyl)carbene, 1-naphthyl(trifluoromethyl)carbene, 4-pyridyl (trifluoromethyl)carbene, 2-pyridyl(trifluoromethyl)carbene, 3-pyridyl (trifluoromethyl)carbene, 3-bromo-5-pyridyl(trifluoromethyl)carbene, meta-phenylbis(trifluoromethyl)carbene and paraphenylbis(trifluoromethyl)carbene in low temperature matrices for the first time. Thenaphthyl(trifluoromethyl)carbenes are photostable and have triplet ground states in matrices asmost of the other studied ary(trifluoromethyl)carbenes. The 1- and 2-naphthyl(trifluoromethyl)diazirines, the precursors of 1- and 2-naphthyl(trifluoromethyl)carbenes, have dissimilar geometric structures leading to differentUV/Vis absorptions. In the studied pyridyl(trifluoromethyl)carbenes, 4-pyridyl(trifluoromethyl)carbene was the most stable one in matrice: no photoproduct from 4-pyridyl(trifluoromethyl)carbene was observed. However, we obtained a small amount ofphotoproducts of 2 - pyridyl(trifluoromethyl)carbene, even though the result was not repeatable.The most reactive isomer was 3 - pyridyl(trifluoromethyl)carbene, which could decompose underprolonged irradiation. The derivative of 3 - pyridyl(trifluoromethyl)carbene, 3 - bromo - 5 -pyridyl(trifluoromethyl)carbene, was more photolabile and could be converted to otherintermediates with comparatively short term irradiation. All the studied pyridylcarbenes havetriplet ground states. Although they were photostable, phenyl(trifluoromethyl)biscarbenesattracted our attention due to their interesting electronic structures. meta-Phenyl(trifluoromethyl)carbene has a quintet ground state, while the overall multiplicity of para- phenyl(trifluoromethyl)carbene is a singlet with a diradical structure.
author: Wang, Pei
keywords: Aryl(trifluoromethyl)carbenes, Heteroaryl(trifluoromethyl)carbenes, Matrix Isolation, Phenylbis(trifluoromethyl)carbenes
date published: 2015
date modified: 2026-07-27T21:47:03Z
provider: University of Nevada - Reno
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: University of Nevada - Reno

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property ID: Handle
value: http://hdl.handle.net/11714/2549