Carbodicarbene Bismaalkene Cations: Unravelling the Complexities of Carbene versus Carbone in Heavy Pnictogen Chemistry

Jacob E. Walley; Levi S. Warring; Guocang Wang; Diane A. Dickie; Sudip Pan; Gernot Frenking; Robert J. Gilliard

doi:10.1002/anie.202014398

Carbodicarbene Bismaalkene Cations: Unravelling the Complexities of Carbene versus Carbone in Heavy Pnictogen Chemistry

Jacob E. Walley, Levi S. Warring, Guocang Wang, Diane A. Dickie, Sudip Pan, Gernot Frenking, Robert J. Gilliard

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Abstract

We report a combined experimental and theoretical study on the first examples of carbodicarbene (CDC)-stabilized bismuth complexes, which feature low-coordinate cationic bismuth centers with C=Bi multiple-bond character. Monocations [(CDC)Bi(Ph)Cl][SbF₆] (8) and [(CDC)BiBr₂(THF)₂][SbF₆] (11), dications [(CDC)Bi(Ph)][SbF₆]₂ (9) and [(CDC)BiBr(THF)₃][NTf₂]₂ (12), and trication [(CDC)₂Bi][NTf₂]₃ (13) have been synthesized via sequential halide abstractions from (CDC)Bi(Ph)Cl₂ (7) and (CDC)BiBr₃ (10). Notably, the dications and trication exhibit C (Formula presented.) Bi double dative bonds and thus represent unprecedented bismaalkene cations. The synthesis of these species highlights a unique non-reductive route to C−Bi π-bonding character. The CDC-[Bi] complexes (7–13) were compared with related NHC-[Bi] complexes (1, 3–6) and show substantially different structural properties. Indeed, the CDC ligand has a remarkable influence on the overall stability of the resulting low-coordinate Bi complexes, suggesting that CDC is a superior ligand to NHC in heavy pnictogen chemistry.

Original language	English
Pages (from-to)	6682-6690
Number of pages	9
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	12
DOIs	https://doi.org/10.1002/anie.202014398
State	Published - 15 Mar 2021
Externally published	Yes

Keywords

bismaalkenes
carbenes
carbodicarbenes
cations
low-coordinate compounds

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10.1002/anie.202014398

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title = "Carbodicarbene Bismaalkene Cations: Unravelling the Complexities of Carbene versus Carbone in Heavy Pnictogen Chemistry",

abstract = "We report a combined experimental and theoretical study on the first examples of carbodicarbene (CDC)-stabilized bismuth complexes, which feature low-coordinate cationic bismuth centers with C=Bi multiple-bond character. Monocations [(CDC)Bi(Ph)Cl][SbF6] (8) and [(CDC)BiBr2(THF)2][SbF6] (11), dications [(CDC)Bi(Ph)][SbF6]2 (9) and [(CDC)BiBr(THF)3][NTf2]2 (12), and trication [(CDC)2Bi][NTf2]3 (13) have been synthesized via sequential halide abstractions from (CDC)Bi(Ph)Cl2 (7) and (CDC)BiBr3 (10). Notably, the dications and trication exhibit C (Formula presented.) Bi double dative bonds and thus represent unprecedented bismaalkene cations. The synthesis of these species highlights a unique non-reductive route to C−Bi π-bonding character. The CDC-[Bi] complexes (7–13) were compared with related NHC-[Bi] complexes (1, 3–6) and show substantially different structural properties. Indeed, the CDC ligand has a remarkable influence on the overall stability of the resulting low-coordinate Bi complexes, suggesting that CDC is a superior ligand to NHC in heavy pnictogen chemistry.",

keywords = "bismaalkenes, carbenes, carbodicarbenes, cations, low-coordinate compounds",

author = "Walley, {Jacob E.} and Warring, {Levi S.} and Guocang Wang and Dickie, {Diane A.} and Sudip Pan and Gernot Frenking and Gilliard, {Robert J.}",

note = "Publisher Copyright: {\textcopyright} 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH",

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T1 - Carbodicarbene Bismaalkene Cations

T2 - Unravelling the Complexities of Carbene versus Carbone in Heavy Pnictogen Chemistry

AU - Walley, Jacob E.

AU - Warring, Levi S.

AU - Wang, Guocang

AU - Dickie, Diane A.

AU - Pan, Sudip

AU - Frenking, Gernot

AU - Gilliard, Robert J.

PY - 2021/3/15

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N2 - We report a combined experimental and theoretical study on the first examples of carbodicarbene (CDC)-stabilized bismuth complexes, which feature low-coordinate cationic bismuth centers with C=Bi multiple-bond character. Monocations [(CDC)Bi(Ph)Cl][SbF6] (8) and [(CDC)BiBr2(THF)2][SbF6] (11), dications [(CDC)Bi(Ph)][SbF6]2 (9) and [(CDC)BiBr(THF)3][NTf2]2 (12), and trication [(CDC)2Bi][NTf2]3 (13) have been synthesized via sequential halide abstractions from (CDC)Bi(Ph)Cl2 (7) and (CDC)BiBr3 (10). Notably, the dications and trication exhibit C (Formula presented.) Bi double dative bonds and thus represent unprecedented bismaalkene cations. The synthesis of these species highlights a unique non-reductive route to C−Bi π-bonding character. The CDC-[Bi] complexes (7–13) were compared with related NHC-[Bi] complexes (1, 3–6) and show substantially different structural properties. Indeed, the CDC ligand has a remarkable influence on the overall stability of the resulting low-coordinate Bi complexes, suggesting that CDC is a superior ligand to NHC in heavy pnictogen chemistry.

AB - We report a combined experimental and theoretical study on the first examples of carbodicarbene (CDC)-stabilized bismuth complexes, which feature low-coordinate cationic bismuth centers with C=Bi multiple-bond character. Monocations [(CDC)Bi(Ph)Cl][SbF6] (8) and [(CDC)BiBr2(THF)2][SbF6] (11), dications [(CDC)Bi(Ph)][SbF6]2 (9) and [(CDC)BiBr(THF)3][NTf2]2 (12), and trication [(CDC)2Bi][NTf2]3 (13) have been synthesized via sequential halide abstractions from (CDC)Bi(Ph)Cl2 (7) and (CDC)BiBr3 (10). Notably, the dications and trication exhibit C (Formula presented.) Bi double dative bonds and thus represent unprecedented bismaalkene cations. The synthesis of these species highlights a unique non-reductive route to C−Bi π-bonding character. The CDC-[Bi] complexes (7–13) were compared with related NHC-[Bi] complexes (1, 3–6) and show substantially different structural properties. Indeed, the CDC ligand has a remarkable influence on the overall stability of the resulting low-coordinate Bi complexes, suggesting that CDC is a superior ligand to NHC in heavy pnictogen chemistry.

KW - bismaalkenes

KW - carbenes

KW - carbodicarbenes

KW - cations

KW - low-coordinate compounds

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SN - 1433-7851

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JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

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ER -

Carbodicarbene Bismaalkene Cations: Unravelling the Complexities of Carbene versus Carbone in Heavy Pnictogen Chemistry

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