Trans Influence of Boryl Ligands in CO2 Hydrogenation on Ruthenium Complexes: Theoretical Prediction of Highly Active Catalysts for CO2 Reduction

In this work, we study the trans influence of boryl ligands and other commonly used non-boryl ligands in order to search for a more active catalyst than the ruthenium dihydride complex Ru(PNP)(CO)H2 for the hydrogenation of CO2. The theoretical calculati...

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Autores principales:	Tian Liu, Zhangyong Liu, Lipeng Tang, Jun Li, Zhuhong Yang
Formato:	article
Lenguaje:	EN
Publicado:	MDPI AG 2021
Materias:	CO<sub>2</sub> hydrogenation trans influence boryl ligand theoretical calculation Chemical technology TP1-1185 Chemistry QD1-999
Acceso en línea:	https://doaj.org/article/7957470d1f50467aa4fdda62a4fb2d1d
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spelling	oai:doaj.org-article:7957470d1f50467aa4fdda62a4fb2d1d2021-11-25T17:06:15ZTrans Influence of Boryl Ligands in CO<sub>2</sub> Hydrogenation on Ruthenium Complexes: Theoretical Prediction of Highly Active Catalysts for CO<sub>2</sub> Reduction10.3390/catal111113562073-4344https://doaj.org/article/7957470d1f50467aa4fdda62a4fb2d1d2021-11-01T00:00:00Zhttps://www.mdpi.com/2073-4344/11/11/1356https://doaj.org/toc/2073-4344In this work, we study the trans influence of boryl ligands and other commonly used non-boryl ligands in order to search for a more active catalyst than the ruthenium dihydride complex Ru(PNP)(CO)H<sub>2</sub> for the hydrogenation of CO<sub>2</sub>. The theoretical calculation results show that only the B ligands exhibit a stronger trans influence than the hydride ligand and are along increasing order of trans influence as follows: –H < –BBr<sub>2</sub> < –BCl<sub>2</sub> ≈ –B(OCH)<sub>2</sub> < –Bcat < –B(OCH<sub>2</sub>)<sub>2</sub> ≈ –B(OH)<sub>2</sub> < –Bpin < –B(NHCH<sub>2</sub>)<sub>2</sub> < –B(OCH<sub>3</sub>)<sub>2</sub> < –B(CH<sub>3</sub>)<sub>2</sub> < –BH<sub>2</sub>. The computed activation free energy for the direct hydride addition to CO<sub>2</sub> and the NBO analysis of the property of the Ru–H bond indicate that the activity of the hydride can be enhanced by the strong trans influence of the B ligands through the change in the Ru–H bond property. The function of the strong trans influence of B ligands is to decrease the d orbital component of Ru in the Ru–H bond. The design of a more active catalyst than the Ru(PNP)(CO)H<sub>2</sub> complex is possible.Tian LiuZhangyong LiuLipeng TangJun LiZhuhong YangMDPI AGarticleCO<sub>2</sub> hydrogenationtrans influenceboryl ligandtheoretical calculationChemical technologyTP1-1185ChemistryQD1-999ENCatalysts, Vol 11, Iss 1356, p 1356 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	CO<sub>2</sub> hydrogenation trans influence boryl ligand theoretical calculation Chemical technology TP1-1185 Chemistry QD1-999
spellingShingle	CO<sub>2</sub> hydrogenation trans influence boryl ligand theoretical calculation Chemical technology TP1-1185 Chemistry QD1-999 Tian Liu Zhangyong Liu Lipeng Tang Jun Li Zhuhong Yang Trans Influence of Boryl Ligands in CO<sub>2</sub> Hydrogenation on Ruthenium Complexes: Theoretical Prediction of Highly Active Catalysts for CO<sub>2</sub> Reduction
description	In this work, we study the trans influence of boryl ligands and other commonly used non-boryl ligands in order to search for a more active catalyst than the ruthenium dihydride complex Ru(PNP)(CO)H<sub>2</sub> for the hydrogenation of CO<sub>2</sub>. The theoretical calculation results show that only the B ligands exhibit a stronger trans influence than the hydride ligand and are along increasing order of trans influence as follows: –H < –BBr<sub>2</sub> < –BCl<sub>2</sub> ≈ –B(OCH)<sub>2</sub> < –Bcat < –B(OCH<sub>2</sub>)<sub>2</sub> ≈ –B(OH)<sub>2</sub> < –Bpin < –B(NHCH<sub>2</sub>)<sub>2</sub> < –B(OCH<sub>3</sub>)<sub>2</sub> < –B(CH<sub>3</sub>)<sub>2</sub> < –BH<sub>2</sub>. The computed activation free energy for the direct hydride addition to CO<sub>2</sub> and the NBO analysis of the property of the Ru–H bond indicate that the activity of the hydride can be enhanced by the strong trans influence of the B ligands through the change in the Ru–H bond property. The function of the strong trans influence of B ligands is to decrease the d orbital component of Ru in the Ru–H bond. The design of a more active catalyst than the Ru(PNP)(CO)H<sub>2</sub> complex is possible.
format	article
author	Tian Liu Zhangyong Liu Lipeng Tang Jun Li Zhuhong Yang
author_facet	Tian Liu Zhangyong Liu Lipeng Tang Jun Li Zhuhong Yang
author_sort	Tian Liu
title	Trans Influence of Boryl Ligands in CO<sub>2</sub> Hydrogenation on Ruthenium Complexes: Theoretical Prediction of Highly Active Catalysts for CO<sub>2</sub> Reduction
title_short	Trans Influence of Boryl Ligands in CO<sub>2</sub> Hydrogenation on Ruthenium Complexes: Theoretical Prediction of Highly Active Catalysts for CO<sub>2</sub> Reduction
title_full	Trans Influence of Boryl Ligands in CO<sub>2</sub> Hydrogenation on Ruthenium Complexes: Theoretical Prediction of Highly Active Catalysts for CO<sub>2</sub> Reduction
title_fullStr	Trans Influence of Boryl Ligands in CO<sub>2</sub> Hydrogenation on Ruthenium Complexes: Theoretical Prediction of Highly Active Catalysts for CO<sub>2</sub> Reduction
title_full_unstemmed	Trans Influence of Boryl Ligands in CO<sub>2</sub> Hydrogenation on Ruthenium Complexes: Theoretical Prediction of Highly Active Catalysts for CO<sub>2</sub> Reduction
title_sort	trans influence of boryl ligands in co<sub>2</sub> hydrogenation on ruthenium complexes: theoretical prediction of highly active catalysts for co<sub>2</sub> reduction
publisher	MDPI AG
publishDate	2021
url	https://doaj.org/article/7957470d1f50467aa4fdda62a4fb2d1d
work_keys_str_mv	AT tianliu transinfluenceofborylligandsincosub2subhydrogenationonrutheniumcomplexestheoreticalpredictionofhighlyactivecatalystsforcosub2subreduction AT zhangyongliu transinfluenceofborylligandsincosub2subhydrogenationonrutheniumcomplexestheoreticalpredictionofhighlyactivecatalystsforcosub2subreduction AT lipengtang transinfluenceofborylligandsincosub2subhydrogenationonrutheniumcomplexestheoreticalpredictionofhighlyactivecatalystsforcosub2subreduction AT junli transinfluenceofborylligandsincosub2subhydrogenationonrutheniumcomplexestheoreticalpredictionofhighlyactivecatalystsforcosub2subreduction AT zhuhongyang transinfluenceofborylligandsincosub2subhydrogenationonrutheniumcomplexestheoreticalpredictionofhighlyactivecatalystsforcosub2subreduction
_version_	1718412720584261632

Trans Influence of Boryl Ligands in CO<sub>2</sub> Hydrogenation on Ruthenium Complexes: Theoretical Prediction of Highly Active Catalysts for CO<sub>2</sub> Reduction

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