Photochemical E-Z isomerization of meta-terphenyl-protected phosphaalkenes and structural characterizations

Vittal B. Gudimetla, Arnold L. Rheingold, John L. Payton, Huo Lei Peng, M. Cather Simpson, John D. Protasiewicz

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

A series of phosphaalkenes, E-ArP=C(H)Ar′ (Ar = 2,6-Mes 2C6H3, Ar′ = Ph (1a); Ar = 2,6-Mes 2C6H3, Ar′ = p-C6H 4Br (2a); Ar = 4-Br-2,6-Mes2C6H2, Ar′ = Ph (3a); Ar = 4-Br-2,6-Mes2C6H2, Ar′ = p-C6H4Br (4a)) have been prepared by phospha-Wittig reactions and characterized. Exposure of these materials either to room light over an extended period of time (days) or to UV light (hours) produced equilibrium mixtures of the E and Z isomers (1b-4b) as indicated by 1H and 31P NMR spectroscopy. The structures of compounds 4a and 4b were determined by single-crystal X-ray diffraction methods. Variable-temperature 1H NMR studies of 4b indicate hindered rotation about the P-CAr bond, with ΔH = 13.8 kcal/mol and ΔS = 1.3 eu. The electronic structures of E- and Z-PhP= C(H)Ph have been examined using density functional theory.

Original languageEnglish (US)
Pages (from-to)4895-4901
Number of pages7
JournalInorganic Chemistry
Volume45
Issue number13
DOIs
StatePublished - Jun 26 2006
Externally publishedYes

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terphenyls
Isomerization
Ultraviolet radiation
Isomers
isomerization
Nuclear magnetic resonance spectroscopy
Electronic structure
Density functional theory
Nuclear magnetic resonance
Single crystals
X ray diffraction
nuclear magnetic resonance
Temperature
rooms
isomers
density functional theory
electronic structure
single crystals
diffraction
spectroscopy

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Gudimetla, V. B., Rheingold, A. L., Payton, J. L., Peng, H. L., Simpson, M. C., & Protasiewicz, J. D. (2006). Photochemical E-Z isomerization of meta-terphenyl-protected phosphaalkenes and structural characterizations. Inorganic Chemistry, 45(13), 4895-4901. https://doi.org/10.1021/ic0520521

Photochemical E-Z isomerization of meta-terphenyl-protected phosphaalkenes and structural characterizations. / Gudimetla, Vittal B.; Rheingold, Arnold L.; Payton, John L.; Peng, Huo Lei; Simpson, M. Cather; Protasiewicz, John D.

In: Inorganic Chemistry, Vol. 45, No. 13, 26.06.2006, p. 4895-4901.

Research output: Contribution to journalArticle

Gudimetla, VB, Rheingold, AL, Payton, JL, Peng, HL, Simpson, MC & Protasiewicz, JD 2006, 'Photochemical E-Z isomerization of meta-terphenyl-protected phosphaalkenes and structural characterizations', Inorganic Chemistry, vol. 45, no. 13, pp. 4895-4901. https://doi.org/10.1021/ic0520521
Gudimetla VB, Rheingold AL, Payton JL, Peng HL, Simpson MC, Protasiewicz JD. Photochemical E-Z isomerization of meta-terphenyl-protected phosphaalkenes and structural characterizations. Inorganic Chemistry. 2006 Jun 26;45(13):4895-4901. https://doi.org/10.1021/ic0520521
Gudimetla, Vittal B. ; Rheingold, Arnold L. ; Payton, John L. ; Peng, Huo Lei ; Simpson, M. Cather ; Protasiewicz, John D. / Photochemical E-Z isomerization of meta-terphenyl-protected phosphaalkenes and structural characterizations. In: Inorganic Chemistry. 2006 ; Vol. 45, No. 13. pp. 4895-4901.
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abstract = "A series of phosphaalkenes, E-ArP=C(H)Ar′ (Ar = 2,6-Mes 2C6H3, Ar′ = Ph (1a); Ar = 2,6-Mes 2C6H3, Ar′ = p-C6H 4Br (2a); Ar = 4-Br-2,6-Mes2C6H2, Ar′ = Ph (3a); Ar = 4-Br-2,6-Mes2C6H2, Ar′ = p-C6H4Br (4a)) have been prepared by phospha-Wittig reactions and characterized. Exposure of these materials either to room light over an extended period of time (days) or to UV light (hours) produced equilibrium mixtures of the E and Z isomers (1b-4b) as indicated by 1H and 31P NMR spectroscopy. The structures of compounds 4a and 4b were determined by single-crystal X-ray diffraction methods. Variable-temperature 1H NMR studies of 4b indicate hindered rotation about the P-CAr bond, with ΔH‡ = 13.8 kcal/mol and ΔS‡ = 1.3 eu. The electronic structures of E- and Z-PhP= C(H)Ph have been examined using density functional theory.",
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