Carbon monoxide insertion at a heavy p-block element: unprecedented formation of a cationic bismuth carbamoyl

Jacqueline Ramler, Jordi Poater, Florian Hirsch, Benedikt Ritschel, Ingo Fischer, F. Matthias Bickelhaupt, Crispin Lichtenberg

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Major advances in the chemistry of 5th and 6th row heavy p-block element compounds have recently uncovered intriguing reactivity patterns towards small molecules such as H 2 , CO 2 , and ethylene. However, well-defined, homogeneous insertion reactions with carbon monoxide, one of the benchmark substrates in this field, have not been reported to date. We demonstrate here, that a cationic bismuth amide undergoes facile insertion of CO into the Bi-N bond under mild conditions. This approach grants direct access to the first cationic bismuth carbamoyl species. Its characterization by NMR, IR, and UV/vis spectroscopy, elemental analysis, single-crystal X-ray analysis, cyclic voltammetry, and DFT calculations revealed intriguing properties, such as a reversible electron transfer at the bismuth center and an absorption feature at 353 nm ascribed to a transition involving σ- and π-type orbitals of the bismuth-carbamoyl functionality. A combined experimental and theoretical approach provided insight into the mechanism of CO insertion. The substrate scope could be extended to isonitriles.

Original languageEnglish
Pages (from-to)4169-4176
Number of pages8
JournalChemical Science
Volume10
Issue number15
Early online date28 Feb 2019
DOIs
Publication statusPublished - 21 Apr 2019

Fingerprint

Bismuth
Carbon Monoxide
X ray analysis
Substrates
Ultraviolet spectroscopy
Discrete Fourier transforms
Amides
Cyclic voltammetry
Nuclear magnetic resonance
Single crystals
Molecules
Electrons
Chemical analysis

Cite this

Ramler, Jacqueline ; Poater, Jordi ; Hirsch, Florian ; Ritschel, Benedikt ; Fischer, Ingo ; Bickelhaupt, F. Matthias ; Lichtenberg, Crispin. / Carbon monoxide insertion at a heavy p-block element : unprecedented formation of a cationic bismuth carbamoyl. In: Chemical Science. 2019 ; Vol. 10, No. 15. pp. 4169-4176.
@article{82fea07637b645d1b09d4e069769d733,
title = "Carbon monoxide insertion at a heavy p-block element: unprecedented formation of a cationic bismuth carbamoyl",
abstract = "Major advances in the chemistry of 5th and 6th row heavy p-block element compounds have recently uncovered intriguing reactivity patterns towards small molecules such as H 2 , CO 2 , and ethylene. However, well-defined, homogeneous insertion reactions with carbon monoxide, one of the benchmark substrates in this field, have not been reported to date. We demonstrate here, that a cationic bismuth amide undergoes facile insertion of CO into the Bi-N bond under mild conditions. This approach grants direct access to the first cationic bismuth carbamoyl species. Its characterization by NMR, IR, and UV/vis spectroscopy, elemental analysis, single-crystal X-ray analysis, cyclic voltammetry, and DFT calculations revealed intriguing properties, such as a reversible electron transfer at the bismuth center and an absorption feature at 353 nm ascribed to a transition involving σ- and π-type orbitals of the bismuth-carbamoyl functionality. A combined experimental and theoretical approach provided insight into the mechanism of CO insertion. The substrate scope could be extended to isonitriles.",
author = "Jacqueline Ramler and Jordi Poater and Florian Hirsch and Benedikt Ritschel and Ingo Fischer and Bickelhaupt, {F. Matthias} and Crispin Lichtenberg",
year = "2019",
month = "4",
day = "21",
doi = "10.1039/C9SC00278B",
language = "English",
volume = "10",
pages = "4169--4176",
journal = "Chemical Science",
issn = "2041-6520",
publisher = "Royal Society of Chemistry",
number = "15",

}

Carbon monoxide insertion at a heavy p-block element : unprecedented formation of a cationic bismuth carbamoyl. / Ramler, Jacqueline; Poater, Jordi; Hirsch, Florian; Ritschel, Benedikt; Fischer, Ingo; Bickelhaupt, F. Matthias; Lichtenberg, Crispin.

In: Chemical Science, Vol. 10, No. 15, 21.04.2019, p. 4169-4176.

Research output: Contribution to JournalArticleAcademicpeer-review

TY - JOUR

T1 - Carbon monoxide insertion at a heavy p-block element

T2 - unprecedented formation of a cationic bismuth carbamoyl

AU - Ramler, Jacqueline

AU - Poater, Jordi

AU - Hirsch, Florian

AU - Ritschel, Benedikt

AU - Fischer, Ingo

AU - Bickelhaupt, F. Matthias

AU - Lichtenberg, Crispin

PY - 2019/4/21

Y1 - 2019/4/21

N2 - Major advances in the chemistry of 5th and 6th row heavy p-block element compounds have recently uncovered intriguing reactivity patterns towards small molecules such as H 2 , CO 2 , and ethylene. However, well-defined, homogeneous insertion reactions with carbon monoxide, one of the benchmark substrates in this field, have not been reported to date. We demonstrate here, that a cationic bismuth amide undergoes facile insertion of CO into the Bi-N bond under mild conditions. This approach grants direct access to the first cationic bismuth carbamoyl species. Its characterization by NMR, IR, and UV/vis spectroscopy, elemental analysis, single-crystal X-ray analysis, cyclic voltammetry, and DFT calculations revealed intriguing properties, such as a reversible electron transfer at the bismuth center and an absorption feature at 353 nm ascribed to a transition involving σ- and π-type orbitals of the bismuth-carbamoyl functionality. A combined experimental and theoretical approach provided insight into the mechanism of CO insertion. The substrate scope could be extended to isonitriles.

AB - Major advances in the chemistry of 5th and 6th row heavy p-block element compounds have recently uncovered intriguing reactivity patterns towards small molecules such as H 2 , CO 2 , and ethylene. However, well-defined, homogeneous insertion reactions with carbon monoxide, one of the benchmark substrates in this field, have not been reported to date. We demonstrate here, that a cationic bismuth amide undergoes facile insertion of CO into the Bi-N bond under mild conditions. This approach grants direct access to the first cationic bismuth carbamoyl species. Its characterization by NMR, IR, and UV/vis spectroscopy, elemental analysis, single-crystal X-ray analysis, cyclic voltammetry, and DFT calculations revealed intriguing properties, such as a reversible electron transfer at the bismuth center and an absorption feature at 353 nm ascribed to a transition involving σ- and π-type orbitals of the bismuth-carbamoyl functionality. A combined experimental and theoretical approach provided insight into the mechanism of CO insertion. The substrate scope could be extended to isonitriles.

UR - http://www.scopus.com/inward/record.url?scp=85063658525&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85063658525&partnerID=8YFLogxK

U2 - 10.1039/C9SC00278B

DO - 10.1039/C9SC00278B

M3 - Article

VL - 10

SP - 4169

EP - 4176

JO - Chemical Science

JF - Chemical Science

SN - 2041-6520

IS - 15

ER -