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Title: 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(Ox Me²)(Ox Me²SiHPh)Im Mes}Rh(H)CO][HB(C₆F₅)₃] (2, Ox Me² = 4,4-dimethyl-2-oxazoline; Im Mes = 1-mesitylimidazole) is synthesized from the neutral rhodium silyl {PhB(Ox Me²)₂Im Mes}RhH(SiH 2Ph)CO (1) and B(C 6F 5) 3. The unusual oxazoline-coordinated silylene structure in 2 is proposed to form by rearrangement of an unobserved isomeric cationic rhodium silylene species [{PhB(Ox Me²)₂Im Mes}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:
 [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
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. doi: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. doi: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 = {2015},
month = {8}
}

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Works referenced in this record:

The hydrodeoxygenation of bioderived furans into alkanes
journal, April 2013

  • Sutton, Andrew D.; Waldie, Fraser D.; Wu, Ruilian
  • Nature Chemistry, Vol. 5, Issue 5, p. 428-432
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