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Bond-Breaking/Bond-Forming Reactions by Vibrational Excitation: Infrared-Induced Bidirectional Tautomerization of Matrix-Isolated Thiotropolone.
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2020-09-01 , DOI: 10.1021/acs.jpclett.0c02272 Cláudio M Nunes 1 , Nelson A M Pereira 1 , Igor Reva 1 , Patrícia S M Amado 2 , Maria L S Cristiano 2 , Rui Fausto 1
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2020-09-01 , DOI: 10.1021/acs.jpclett.0c02272 Cláudio M Nunes 1 , Nelson A M Pereira 1 , Igor Reva 1 , Patrícia S M Amado 2 , Maria L S Cristiano 2 , Rui Fausto 1
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Infrared vibrational excitation is a promising approach for gaining exceptional control of chemical reactions, in ways that cannot be attained via thermal or electronic excitation. Here, we report an unprecedented example of a bond-breaking/bond-forming reaction by vibrational excitation under matrix isolation conditions. Thiotropolone monomers were isolated in cryogenic argon matrices and characterized by infrared spectroscopy and vibrational computations (harmonic and anharmonic). Narrowband near-infrared irradiations tuned at frequencies of first CH stretching overtone (5940 cm–1) or combination modes (5980 cm–1) of the OH tautomer, the sole form of the compound that exists in the as-deposited matrices, led to its conversion into the SH tautomer. The tautomerization in the reverse direction was achieved by vibrational excitation of the SH tautomer with irradiation at 5947 or 5994 cm–1, corresponding to the frequencies of its CH stretching combination and overtone modes. This pioneer demonstration of bidirectional hydroxyl ↔ thiol tautomerization controlled by vibrational excitation creates prospects for new advances in vibrationally induced chemistry.
中文翻译：
振动激发的成键断裂/键形成反应：基质分离的噻咯烷酮的红外诱导双向互变异构。
红外振动激发是一种获得化学反应异常控制的有前途的方法，其方式是通过热激发或电子激发无法实现的。在这里，我们报道了在基质隔离条件下通过振动激发进行键断裂/键形成反应的空前实例。在低温氩气基质中分离了噻吩酮单体，并通过红外光谱和振动计算（谐波和非谐波）进行了表征。在第一个CH拉伸泛音（5940 cm –1）或组合模式（5980 cm –1）的频率下调谐的窄带近红外辐射）OH互变异构体（存在于沉积基质中的化合物的唯一形式）导致其转化为SH互变异构体。反向互变异构是通过SH互变异构体在5947或5994 cm –1的辐射下的振动激发而实现的，对应于其CH拉伸组合的频率和泛音模式。由振动激发控制的双向羟基↔硫醇互变异构的这一先驱性演示为振动诱导化学的新进展创造了前景。
更新日期：2020-10-02
中文翻译：
振动激发的成键断裂/键形成反应：基质分离的噻咯烷酮的红外诱导双向互变异构。
红外振动激发是一种获得化学反应异常控制的有前途的方法，其方式是通过热激发或电子激发无法实现的。在这里，我们报道了在基质隔离条件下通过振动激发进行键断裂/键形成反应的空前实例。在低温氩气基质中分离了噻吩酮单体，并通过红外光谱和振动计算（谐波和非谐波）进行了表征。在第一个CH拉伸泛音（5940 cm –1）或组合模式（5980 cm –1）的频率下调谐的窄带近红外辐射）OH互变异构体（存在于沉积基质中的化合物的唯一形式）导致其转化为SH互变异构体。反向互变异构是通过SH互变异构体在5947或5994 cm –1的辐射下的振动激发而实现的，对应于其CH拉伸组合的频率和泛音模式。由振动激发控制的双向羟基↔硫醇互变异构的这一先驱性演示为振动诱导化学的新进展创造了前景。
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