Mild partial deoxygenation of esters catalyzed by an oxazolinylborate-coordinated rhodium silylene
Abstract
An electrophilic, coordinatively unsaturated rhodium complex supported by borate-linked oxazoline, oxazoline-coordinated silylene, and N-heterocyclic carbene donors [{κ³-N,Si,C-PhB(OxMe²)(OxMe²SiHPh)ImMes}Rh(H)CO][HB(C₆F₅)₃] (2, OxMe² = 4,4-dimethyl-2-oxazoline; ImMes = 1-mesitylimidazole) is synthesized from the neutral rhodium silyl {PhB(OxMe²)₂ImMes}RhH(SiH2Ph)CO (1) and B(C6F5)3. The unusual oxazoline-coordinated silylene structure in 2 is proposed to form by rearrangement of an unobserved isomeric cationic rhodium silylene species [{PhB(OxMe²)₂ImMes}RhH(SiHPh)CO][HB(C₆F₅)₃] generated by H abstraction. Complex 2 catalyzes reductions of organic carbonyl compounds with silanes to give hydrosilylation products or deoxygenation products. The pathway to these reactions is primarily influenced by the degree of substitution of the organosilane. Reactions with primary silanes give deoxygenation of esters to ethers, amides to amines, and ketones and aldehydes to hydrocarbons, whereas tertiary silanes react to give 1,2-hydrosilylation of the carbonyl functionality. In contrast, the strong Lewis acid B(C₆F₅)₃ catalyzes the complete deoxygenation of carbonyl compounds to hydrocarbons with PhSiH₃ as the reducing agent.
- Authors:
-
- Iowa State Univ., Ames, IA (United States)
- Publication Date:
- Research Org.:
- Ames Lab., Ames, IA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1221625
- Report Number(s):
- IS-J-8724
Journal ID: ISSN 1477-9226; ICHBD9
- Grant/Contract Number:
- AC02-07CH11358; W-7405-ENG-82
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Dalton Transactions
- Additional Journal Information:
- Journal Volume: 44; Journal Issue: 36; Journal ID: ISSN 1477-9226
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Xu, Songchen, Boschen, Jeffery S., Biswas, Abhranil, Kobayashi, Takeshi, Pruski, Marek, Windus, Theresa L., and Sadow, Aaron D. Mild partial deoxygenation of esters catalyzed by an oxazolinylborate-coordinated rhodium silylene. United States: N. p., 2015.
Web. doi:10.1039/C5DT02844B.
Xu, Songchen, Boschen, Jeffery S., Biswas, Abhranil, Kobayashi, Takeshi, Pruski, Marek, Windus, Theresa L., & Sadow, Aaron D. Mild partial deoxygenation of esters catalyzed by an oxazolinylborate-coordinated rhodium silylene. United States. https://doi.org/10.1039/C5DT02844B
Xu, Songchen, Boschen, Jeffery S., Biswas, Abhranil, Kobayashi, Takeshi, Pruski, Marek, Windus, Theresa L., and Sadow, Aaron D. Mon .
"Mild partial deoxygenation of esters catalyzed by an oxazolinylborate-coordinated rhodium silylene". United States. https://doi.org/10.1039/C5DT02844B. https://www.osti.gov/servlets/purl/1221625.
@article{osti_1221625,
title = {Mild partial deoxygenation of esters catalyzed by an oxazolinylborate-coordinated rhodium silylene},
author = {Xu, Songchen and Boschen, Jeffery S. and Biswas, Abhranil and Kobayashi, Takeshi and Pruski, Marek and Windus, Theresa L. and Sadow, Aaron D.},
abstractNote = {An electrophilic, coordinatively unsaturated rhodium complex supported by borate-linked oxazoline, oxazoline-coordinated silylene, and N-heterocyclic carbene donors [{κ³-N,Si,C-PhB(OxMe²)(OxMe²SiHPh)ImMes}Rh(H)CO][HB(C₆F₅)₃] (2, OxMe² = 4,4-dimethyl-2-oxazoline; ImMes = 1-mesitylimidazole) is synthesized from the neutral rhodium silyl {PhB(OxMe²)₂ImMes}RhH(SiH2Ph)CO (1) and B(C6F5)3. The unusual oxazoline-coordinated silylene structure in 2 is proposed to form by rearrangement of an unobserved isomeric cationic rhodium silylene species [{PhB(OxMe²)₂ImMes}RhH(SiHPh)CO][HB(C₆F₅)₃] generated by H abstraction. Complex 2 catalyzes reductions of organic carbonyl compounds with silanes to give hydrosilylation products or deoxygenation products. The pathway to these reactions is primarily influenced by the degree of substitution of the organosilane. Reactions with primary silanes give deoxygenation of esters to ethers, amides to amines, and ketones and aldehydes to hydrocarbons, whereas tertiary silanes react to give 1,2-hydrosilylation of the carbonyl functionality. In contrast, the strong Lewis acid B(C₆F₅)₃ catalyzes the complete deoxygenation of carbonyl compounds to hydrocarbons with PhSiH₃ as the reducing agent.},
doi = {10.1039/C5DT02844B},
journal = {Dalton Transactions},
number = 36,
volume = 44,
place = {United States},
year = {Mon Aug 17 00:00:00 EDT 2015},
month = {Mon Aug 17 00:00:00 EDT 2015}
}
Web of Science
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