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Issue 27, 2020, Issue in Progress
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Carbon monoxide formation from trimethylamine-boranecarboxylate: DFT studies of SNi and chelotropic mechanisms

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Abstract

Trimethylamine-boranecarboxylic acid (CH3)3N-BH2COOH and other amine carboxyboranes have been observed to undergo slow decarbonylation in neutral aqueous solution. This reaction, when it occurs in vivo, may have a therapeutic effect by delivering low concentrations of carbon monoxide over an extended period. In order to identify a possible mechanistic pathway for decarbonylation, the smallest tertiary amine derivative and its corresponding carboxylate ion were studied using CCSD(T)/PCM/6-311++G(2d,p)//M06-2X/PCM/6-311++G(2d,p) model chemistry. The proposed mechanistic pathway begins with a trimethylamine boranecarboxylate ion, which first undergoes an internal substitution reaction (SNi) to give free amine and the carboxyborane anion BH2COO. The latter cyclic ion then releases CO via a rapid chelotropic fragmentation. The role of water solvent in these reactions was explored by structural and energetic analysis of hydrogen-bonded complexes. It was found that complexation with water inhibits dissociation of trimethylamine by stabilizing the trimethylamine carboxyborane anion, whereas water accelerates CO loss by stabilizing the polar chelotropic transition state.

Graphical abstract: Carbon monoxide formation from trimethylamine-boranecarboxylate: DFT studies of SNi and chelotropic mechanisms

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Supplementary files

Article information


Submitted
18 Feb 2020
Accepted
15 Apr 2020
First published
24 Apr 2020

This article is Open Access

RSC Adv., 2020,10, 16038-16044
Article type
Paper

Carbon monoxide formation from trimethylamine-boranecarboxylate: DFT studies of SNi and chelotropic mechanisms

J. W. Keller, T. I. Ayudhya and N. N. Dingra, RSC Adv., 2020, 10, 16038
DOI: 10.1039/D0RA01572E

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