Photoinduced Sulfur-Nitrogen Bond Rotation and Thermal Nitrogen Inversion in Heterocumulene OSNSO

Zhuang Wu; Ruijuan Feng; Jian Xu; Yan Lu; Bo Lu; Tao Yang; Gernot Frenking; Tarek Trabelsi; Joseph S. Francisco; Xiaoqing Zeng

doi:10.1021/jacs.7b12622

Photoinduced Sulfur-Nitrogen Bond Rotation and Thermal Nitrogen Inversion in Heterocumulene OSNSO

Zhuang Wu, Ruijuan Feng, Jian Xu, Yan Lu, Bo Lu, Tao Yang, Gernot Frenking, Tarek Trabelsi, Joseph S. Francisco, Xiaoqing Zeng

School of Chemistry and Moleculai Engineering

Research output: Contribution to journal › Article › peer-review

9 Scopus citations

Abstract

An exotic ternary S, N, O heterocumulene OSNSO in syn-syn (A) and syn-anti (B) conformations has been generated in the gas phase through flash vacuum pyrolysis of CF₃S(O)NSO at 700 K. Upon visible light irradiation (570 ± 20 or 532 nm), both A and B, isolated in cryogenic matrices (N₂, Ne, Ar, and Kr, <30 K), convert to a higher-energy anti-anti conformer (C). The reverse conformational transformation occurs either through S=N bond rotation (C to A and B) under visible light irradiation (400 ± 20 nm) at 2.8 K or through thermal nitrogen inversion (C to A) in the temperature range of 20-30 K, for which an exceptionally low activation barrier of 1.18 ± 0.07 kcal mol^-1 has been experimentally determined.

Original language	English
Pages (from-to)	1231-1234
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	140
Issue number	4
DOIs	https://doi.org/10.1021/jacs.7b12622
State	Published - 31 Jan 2018

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title = "Photoinduced Sulfur-Nitrogen Bond Rotation and Thermal Nitrogen Inversion in Heterocumulene OSNSO",

abstract = "An exotic ternary S, N, O heterocumulene OSNSO in syn-syn (A) and syn-anti (B) conformations has been generated in the gas phase through flash vacuum pyrolysis of CF3S(O)NSO at 700 K. Upon visible light irradiation (570 ± 20 or 532 nm), both A and B, isolated in cryogenic matrices (N2, Ne, Ar, and Kr, <30 K), convert to a higher-energy anti-anti conformer (C). The reverse conformational transformation occurs either through S=N bond rotation (C to A and B) under visible light irradiation (400 ± 20 nm) at 2.8 K or through thermal nitrogen inversion (C to A) in the temperature range of 20-30 K, for which an exceptionally low activation barrier of 1.18 ± 0.07 kcal mol-1 has been experimentally determined.",

author = "Zhuang Wu and Ruijuan Feng and Jian Xu and Yan Lu and Bo Lu and Tao Yang and Gernot Frenking and Tarek Trabelsi and Francisco, {Joseph S.} and Xiaoqing Zeng",

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day = "31",

doi = "10.1021/jacs.7b12622",

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T1 - Photoinduced Sulfur-Nitrogen Bond Rotation and Thermal Nitrogen Inversion in Heterocumulene OSNSO

AU - Wu, Zhuang

AU - Feng, Ruijuan

AU - Xu, Jian

AU - Lu, Yan

AU - Lu, Bo

AU - Yang, Tao

AU - Frenking, Gernot

AU - Trabelsi, Tarek

AU - Francisco, Joseph S.

AU - Zeng, Xiaoqing

PY - 2018/1/31

Y1 - 2018/1/31

N2 - An exotic ternary S, N, O heterocumulene OSNSO in syn-syn (A) and syn-anti (B) conformations has been generated in the gas phase through flash vacuum pyrolysis of CF3S(O)NSO at 700 K. Upon visible light irradiation (570 ± 20 or 532 nm), both A and B, isolated in cryogenic matrices (N2, Ne, Ar, and Kr, <30 K), convert to a higher-energy anti-anti conformer (C). The reverse conformational transformation occurs either through S=N bond rotation (C to A and B) under visible light irradiation (400 ± 20 nm) at 2.8 K or through thermal nitrogen inversion (C to A) in the temperature range of 20-30 K, for which an exceptionally low activation barrier of 1.18 ± 0.07 kcal mol-1 has been experimentally determined.

AB - An exotic ternary S, N, O heterocumulene OSNSO in syn-syn (A) and syn-anti (B) conformations has been generated in the gas phase through flash vacuum pyrolysis of CF3S(O)NSO at 700 K. Upon visible light irradiation (570 ± 20 or 532 nm), both A and B, isolated in cryogenic matrices (N2, Ne, Ar, and Kr, <30 K), convert to a higher-energy anti-anti conformer (C). The reverse conformational transformation occurs either through S=N bond rotation (C to A and B) under visible light irradiation (400 ± 20 nm) at 2.8 K or through thermal nitrogen inversion (C to A) in the temperature range of 20-30 K, for which an exceptionally low activation barrier of 1.18 ± 0.07 kcal mol-1 has been experimentally determined.

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DO - 10.1021/jacs.7b12622

M3 - 文章

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SN - 0002-7863

VL - 140

SP - 1231

EP - 1234

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 4

ER -

Photoinduced Sulfur-Nitrogen Bond Rotation and Thermal Nitrogen Inversion in Heterocumulene OSNSO

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