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

Tondreau, Aaron M.; Michalczyk, Ryszard; Boncella, James M.

doi:10.1021/acs.organomet.7b00618

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

Journal Article · Wed Sep 20 00:00:00 EDT 2017 · Organometallics

DOI:https://doi.org/10.1021/acs.organomet.7b00618· OSTI ID:1438107

Tondreau, Aaron M. ^[1]; Michalczyk, Ryszard ^[1];

^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

(^iPrPN^HP)Mn(CO)₂(OH) (2; ^iPrPN^HP = 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 (^iPrPN^HP)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.

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Research Organization:: Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC52-06NA25396

OSTI ID:: 1438107

Report Number(s):: LA-UR-17-23639

Journal Information:: Organometallics, Vol. 36, Issue 21; ISSN 0276-7333

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 18 works

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