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Title: Reversible 1,2-Addition of Water To Form a Nucleophilic Mn(I) Hydroxide Complex: A Thermodynamic and Reactivity Study

Abstract

( iPrPN HP)Mn(CO) 2(OH) (2; iPrPN HP = HN{CH 2CH 2(P iPr 2)} 2) was formed from the reversible 1,2-addition of water to ( iPrPNP)Mn(CO) 2 (1; iPrPNP = the deprotonated, amide form of the ligand, –N{CH 2CH 2(P iPr 2)} 2). This reversible reaction was probed via variable-temperature NMR experiments, and the energetics of the 1,2-addition/elimination was found to be slightly exothermic (-0.8 kcal/mol). The corresponding manganese hydroxide was found to react with aldehydes, yielding the corresponding manganese carboxylate complexes ( iPrPN HP)Mn(CO) 2(CO 2R), where R = H, methyl, phenyl. While no reaction between 1 and neat benzaldehyde was observed, in the presence of water, conversion to the corresponding manganese-bound benzoate with formation of H 2 was observed. The catalytic oxidation of benzaldehyde by water without additives was unsuccessful due to strong product inhibition, with the manganese benzoate formed under a variety of reaction conditions. Upon addition of base, a catalytic cycle for the conversion of aldehyde to carboxylate and hydrogen can be devised.

Authors:
 [1];  [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1438107
Report Number(s):
LA-UR-17-23639
Journal ID: ISSN 0276-7333
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 36; Journal Issue: 21; Journal ID: ISSN 0276-7333
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Tondreau, Aaron M., Michalczyk, Ryszard, and Boncella, James M. Reversible 1,2-Addition of Water To Form a Nucleophilic Mn(I) Hydroxide Complex: A Thermodynamic and Reactivity Study. United States: N. p., 2017. Web. doi:10.1021/acs.organomet.7b00618.
Tondreau, Aaron M., Michalczyk, Ryszard, & Boncella, James M. Reversible 1,2-Addition of Water To Form a Nucleophilic Mn(I) Hydroxide Complex: A Thermodynamic and Reactivity Study. United States. doi:10.1021/acs.organomet.7b00618.
Tondreau, Aaron M., Michalczyk, Ryszard, and Boncella, James M. Wed . "Reversible 1,2-Addition of Water To Form a Nucleophilic Mn(I) Hydroxide Complex: A Thermodynamic and Reactivity Study". United States. doi:10.1021/acs.organomet.7b00618. https://www.osti.gov/servlets/purl/1438107.
@article{osti_1438107,
title = {Reversible 1,2-Addition of Water To Form a Nucleophilic Mn(I) Hydroxide Complex: A Thermodynamic and Reactivity Study},
author = {Tondreau, Aaron M. and Michalczyk, Ryszard and Boncella, James M.},
abstractNote = {(iPrPNHP)Mn(CO)2(OH) (2; iPrPNHP = HN{CH2CH2(PiPr2)}2) was formed from the reversible 1,2-addition of water to (iPrPNP)Mn(CO)2 (1; iPrPNP = the deprotonated, amide form of the ligand, –N{CH2CH2(PiPr2)}2). This reversible reaction was probed via variable-temperature NMR experiments, and the energetics of the 1,2-addition/elimination was found to be slightly exothermic (-0.8 kcal/mol). The corresponding manganese hydroxide was found to react with aldehydes, yielding the corresponding manganese carboxylate complexes (iPrPNHP)Mn(CO)2(CO2R), where R = H, methyl, phenyl. While no reaction between 1 and neat benzaldehyde was observed, in the presence of water, conversion to the corresponding manganese-bound benzoate with formation of H2 was observed. The catalytic oxidation of benzaldehyde by water without additives was unsuccessful due to strong product inhibition, with the manganese benzoate formed under a variety of reaction conditions. Upon addition of base, a catalytic cycle for the conversion of aldehyde to carboxylate and hydrogen can be devised.},
doi = {10.1021/acs.organomet.7b00618},
journal = {Organometallics},
issn = {0276-7333},
number = 21,
volume = 36,
place = {United States},
year = {2017},
month = {9}
}

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Works referencing / citing this record:

Reversible homolytic activation of water via metal–ligand cooperativity in a T-shaped Ni( ii ) complex
journal, January 2019

  • Chang, Mu-Chieh; Jesse, Kate A.; Filatov, Alexander S.
  • Chemical Science, Vol. 10, Issue 5
  • DOI: 10.1039/c8sc03719a

Reversible homolytic activation of water via metal–ligand cooperativity in a T-shaped Ni( ii ) complex
journal, January 2019

  • Chang, Mu-Chieh; Jesse, Kate A.; Filatov, Alexander S.
  • Chemical Science, Vol. 10, Issue 5
  • DOI: 10.1039/c8sc03719a