Reactivity of Silanes with (tBuPONOP)Ruthenium Dichloride: Facile Synthesis of Chloro-Silyl Ruthenium Compounds and Formic Acid Decomposition
Abstract
The coordination of tBuPONOP (tBuPONOP=2,6-bis(ditert-butylphosphinito)pyridine) to different ruthenium starting materials, to generate (tBuPONOP)RuCl2, was investigated in this paper. The resultant (tBuPONOP)RuCl2 reactivity with three different silanes was then investigated and contrasted dramatically with the reactivity of (iPrPONOP)RuCl2(DMSO) (iPrPONOP=2,6-bis(diisopropylphosphinito)pyridine) with the same silanes. The 16-electron species (tBuPONOP)Ru(H)Cl was produced from the reaction of triethylsilane with (tBuPONOP)RuCl2. Reactions of (tBuPONOP)RuCl2 with both phenylsilane or diphenylsilane afforded the 16-electron hydrido-silyl species (tBuPONOP)Ru(H)(PhSiCl2) and (tBuPONOP)Ru(H)(Ph2SiCl), respectively. Reactions of all three of these complexes with silver triflate afforded the simple salt metathesis products of (tBuPONOP)Ru(H)(OTf), (tBuPONOP)Ru(H)(PhSiCl(OTf)), and (tBuPONOP)Ru(H)(Ph2Si(OTf)). Formic acid dehydrogenation was performed in the presence of triethylamine (TEA), and each species proved competent for gas-pressure generation of CO2 and H2. Finally, the hydride species (tBuPONOP)Ru(H)Cl, (tBuPONOP)Ru(H)(OTf), and (tBuPONOP)Ru(H)(PhSiCl2) exhibited faster catalytic activity than the other compounds tested.
- Publication Date:
- Research Org.:
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1435519
- Report Number(s):
- LA-UR-17-25821
Journal ID: ISSN 0947-6539
- Grant/Contract Number:
- AC52-06NA25396
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry - A European Journal
- Additional Journal Information:
- Journal Volume: 23; Journal Issue: 55; Journal ID: ISSN 0947-6539
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; dehydrogenation; formic acid; PONOP ligand; ruthenium; silyl group
Citation Formats
Anderson, Nickolas H., Boncella, James M., and Tondreau, Aaron M. Reactivity of Silanes with (tBuPONOP)Ruthenium Dichloride: Facile Synthesis of Chloro-Silyl Ruthenium Compounds and Formic Acid Decomposition. United States: N. p., 2017.
Web. doi:10.1002/chem.201703722.
Anderson, Nickolas H., Boncella, James M., & Tondreau, Aaron M. Reactivity of Silanes with (tBuPONOP)Ruthenium Dichloride: Facile Synthesis of Chloro-Silyl Ruthenium Compounds and Formic Acid Decomposition. United States. https://doi.org/10.1002/chem.201703722
Anderson, Nickolas H., Boncella, James M., and Tondreau, Aaron M. Tue .
"Reactivity of Silanes with (tBuPONOP)Ruthenium Dichloride: Facile Synthesis of Chloro-Silyl Ruthenium Compounds and Formic Acid Decomposition". United States. https://doi.org/10.1002/chem.201703722. https://www.osti.gov/servlets/purl/1435519.
@article{osti_1435519,
title = {Reactivity of Silanes with (tBuPONOP)Ruthenium Dichloride: Facile Synthesis of Chloro-Silyl Ruthenium Compounds and Formic Acid Decomposition},
author = {Anderson, Nickolas H. and Boncella, James M. and Tondreau, Aaron M.},
abstractNote = {The coordination of tBuPONOP (tBuPONOP=2,6-bis(ditert-butylphosphinito)pyridine) to different ruthenium starting materials, to generate (tBuPONOP)RuCl2, was investigated in this paper. The resultant (tBuPONOP)RuCl2 reactivity with three different silanes was then investigated and contrasted dramatically with the reactivity of (iPrPONOP)RuCl2(DMSO) (iPrPONOP=2,6-bis(diisopropylphosphinito)pyridine) with the same silanes. The 16-electron species (tBuPONOP)Ru(H)Cl was produced from the reaction of triethylsilane with (tBuPONOP)RuCl2. Reactions of (tBuPONOP)RuCl2 with both phenylsilane or diphenylsilane afforded the 16-electron hydrido-silyl species (tBuPONOP)Ru(H)(PhSiCl2) and (tBuPONOP)Ru(H)(Ph2SiCl), respectively. Reactions of all three of these complexes with silver triflate afforded the simple salt metathesis products of (tBuPONOP)Ru(H)(OTf), (tBuPONOP)Ru(H)(PhSiCl(OTf)), and (tBuPONOP)Ru(H)(Ph2Si(OTf)). Formic acid dehydrogenation was performed in the presence of triethylamine (TEA), and each species proved competent for gas-pressure generation of CO2 and H2. Finally, the hydride species (tBuPONOP)Ru(H)Cl, (tBuPONOP)Ru(H)(OTf), and (tBuPONOP)Ru(H)(PhSiCl2) exhibited faster catalytic activity than the other compounds tested.},
doi = {10.1002/chem.201703722},
journal = {Chemistry - A European Journal},
number = 55,
volume = 23,
place = {United States},
year = {Tue Aug 15 00:00:00 EDT 2017},
month = {Tue Aug 15 00:00:00 EDT 2017}
}
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Cited by: 11 works
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Figures / Tables:
Figure 1: The coordinatively unsaturated compounds: a) (tBuPONOP)Ru(CO), b) (tBuPONOP)Ru(CO)2, c) (tBuPONOP)Ru(H)Cl, and d) (tBuPONOP)RuCl2 (1) by Milstein.
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Works referencing / citing this record:
A General, Activator-Free Palladium-Catalyzed Synthesis of Arylacetic and Benzoic Acids from Formic Acid
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