Synthesis, structure, and thermochemistry of adduct formation between N-heterocyclic carbenes and isocyanates or mesitylnitrile oxide

Manuel Temprado; Subhojit Majumdar; Xiaochen Cai; Burjor Captain; Carl D. Hoff

doi:10.1007/s11224-013-0305-2

Synthesis, structure, and thermochemistry of adduct formation between N-heterocyclic carbenes and isocyanates or mesitylnitrile oxide

Manuel Temprado, Subhojit Majumdar, Xiaochen Cai, Burjor Captain, Carl D. Hoff

Chemistry

Research output: Contribution to journal › Article › peer-review

9 Scopus citations

Abstract

Reaction of N-heterocyclic carbenes (NHCs) with isocyanates yields stable zwitterionic imidates/amidates in toluene solution. These compounds were fully characterized and the crystal structures of several species were determined by X-ray crystallography. The thermochemistry of binding of these and related species was studied by solution calorimetry. Comparison is made of the enthalpies of binding of NHC to isocyanates (RNCO) and isomeric nitrile oxides (RCNO) as well as CO₂. DFT calculations were performed to additionally assess the nature of bonding in these compounds.

Original language	English (US)
Pages (from-to)	2059-2068
Number of pages	10
Journal	Structural Chemistry
Volume	24
Issue number	6
DOIs	https://doi.org/10.1007/s11224-013-0305-2
State	Published - Dec 2013

Keywords

Betaines
Carbenes
NHC
Thermochemistry
Zwitterions

ASJC Scopus subject areas

Condensed Matter Physics
Physical and Theoretical Chemistry

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title = "Synthesis, structure, and thermochemistry of adduct formation between N-heterocyclic carbenes and isocyanates or mesitylnitrile oxide",

abstract = "Reaction of N-heterocyclic carbenes (NHCs) with isocyanates yields stable zwitterionic imidates/amidates in toluene solution. These compounds were fully characterized and the crystal structures of several species were determined by X-ray crystallography. The thermochemistry of binding of these and related species was studied by solution calorimetry. Comparison is made of the enthalpies of binding of NHC to isocyanates (RNCO) and isomeric nitrile oxides (RCNO) as well as CO2. DFT calculations were performed to additionally assess the nature of bonding in these compounds.",

keywords = "Betaines, Carbenes, NHC, Thermochemistry, Zwitterions",

author = "Manuel Temprado and Subhojit Majumdar and Xiaochen Cai and Burjor Captain and Hoff, {Carl D.}",

note = "Funding Information: Acknowledgments Support of this work by the National Science Foundation Grant CHE 0615743 (C. D. H.) and by the Spanish Ministry of Economy and Competitiveness (MINECO) under CTQ2012-36966 (M. T.) is gratefully acknowledged. The authors thank Professor Janis Louie at the University of Utah for helpful discussions.",

year = "2013",

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language = "English (US)",

volume = "24",

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journal = "Structural Chemistry",

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T1 - Synthesis, structure, and thermochemistry of adduct formation between N-heterocyclic carbenes and isocyanates or mesitylnitrile oxide

AU - Temprado, Manuel

AU - Majumdar, Subhojit

AU - Cai, Xiaochen

AU - Captain, Burjor

AU - Hoff, Carl D.

N1 - Funding Information: Acknowledgments Support of this work by the National Science Foundation Grant CHE 0615743 (C. D. H.) and by the Spanish Ministry of Economy and Competitiveness (MINECO) under CTQ2012-36966 (M. T.) is gratefully acknowledged. The authors thank Professor Janis Louie at the University of Utah for helpful discussions.

PY - 2013/12

Y1 - 2013/12

N2 - Reaction of N-heterocyclic carbenes (NHCs) with isocyanates yields stable zwitterionic imidates/amidates in toluene solution. These compounds were fully characterized and the crystal structures of several species were determined by X-ray crystallography. The thermochemistry of binding of these and related species was studied by solution calorimetry. Comparison is made of the enthalpies of binding of NHC to isocyanates (RNCO) and isomeric nitrile oxides (RCNO) as well as CO2. DFT calculations were performed to additionally assess the nature of bonding in these compounds.

AB - Reaction of N-heterocyclic carbenes (NHCs) with isocyanates yields stable zwitterionic imidates/amidates in toluene solution. These compounds were fully characterized and the crystal structures of several species were determined by X-ray crystallography. The thermochemistry of binding of these and related species was studied by solution calorimetry. Comparison is made of the enthalpies of binding of NHC to isocyanates (RNCO) and isomeric nitrile oxides (RCNO) as well as CO2. DFT calculations were performed to additionally assess the nature of bonding in these compounds.

KW - Betaines

KW - Carbenes

KW - NHC

KW - Thermochemistry

KW - Zwitterions

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DO - 10.1007/s11224-013-0305-2

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VL - 24

SP - 2059

EP - 2068

JO - Structural Chemistry

JF - Structural Chemistry

SN - 1040-0400

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