A Pyridine-Stabilized N-Phosphinoamidinato N-Heterocyclic Carbene-Diboravinyl Cation: Boron Analogue of Vinyl Cation

Jun Fan; Pei Ting Chia; Zheng Feng Zhang; Ming Chung Yang; Ming Der Su; Cheuk Wai So

doi:10.1002/anie.202212842

A Pyridine-Stabilized N-Phosphinoamidinato N-Heterocyclic Carbene-Diboravinyl Cation: Boron Analogue of Vinyl Cation

Jun Fan, Pei Ting Chia, Zheng Feng Zhang, Ming Chung Yang, Ming Der Su^*, Cheuk Wai So^*

^*Corresponding author for this work

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

7 Citations (Scopus)

Abstract

A boron analogue of vinyl cation, pyridine-stabilized N-phosphinoamidinato N-heterocyclic carbene (NHC)-diboravinyl cation 2⁺, was synthesized by displacement of bromide in diborene 1 with excess pyridine. Experimental and computational studies showed that the positive charge is mainly at the B−B skeleton with delocalization to the pyridine ligand. One of the main modes of reactivity is through the B=B double bond alongside activation of the pyridine substituent, where the B_pyridine center is the predominant nucleophilic center and the predominant electrophilic center is either the activated pyridine para position or the B_NHC center, illustrating the presence of diborene cation A, borylene-borenium cation B and diborene-pyridinium cation C resonance structures in cation 2⁺.

Original language	English
Article number	e202212842
Journal	Angewandte Chemie - International Edition
Volume	61
Issue number	46
DOIs	https://doi.org/10.1002/anie.202212842
Publication status	Published - Nov 14 2022
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2022 Wiley-VCH GmbH.

ASJC Scopus Subject Areas

Catalysis
General Chemistry

Keywords

Boron
Diborene
Small Molecule Activation
Vinyl Cation

Access to Document

10.1002/anie.202212842

Cite this

@article{8ca7e6dd31804e049e3a256d0b0fe0e9,

title = "A Pyridine-Stabilized N-Phosphinoamidinato N-Heterocyclic Carbene-Diboravinyl Cation: Boron Analogue of Vinyl Cation",

abstract = "A boron analogue of vinyl cation, pyridine-stabilized N-phosphinoamidinato N-heterocyclic carbene (NHC)-diboravinyl cation 2+, was synthesized by displacement of bromide in diborene 1 with excess pyridine. Experimental and computational studies showed that the positive charge is mainly at the B−B skeleton with delocalization to the pyridine ligand. One of the main modes of reactivity is through the B=B double bond alongside activation of the pyridine substituent, where the Bpyridine center is the predominant nucleophilic center and the predominant electrophilic center is either the activated pyridine para position or the BNHC center, illustrating the presence of diborene cation A, borylene-borenium cation B and diborene-pyridinium cation C resonance structures in cation 2+.",

keywords = "Boron, Diborene, Small Molecule Activation, Vinyl Cation",

author = "Jun Fan and Chia, \{Pei Ting\} and Zhang, \{Zheng Feng\} and Yang, \{Ming Chung\} and Su, \{Ming Der\} and So, \{Cheuk Wai\}",

note = "Publisher Copyright: {\textcopyright} 2022 Wiley-VCH GmbH.",

year = "2022",

month = nov,

day = "14",

doi = "10.1002/anie.202212842",

language = "English",

volume = "61",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

number = "46",

}

TY - JOUR

T1 - A Pyridine-Stabilized N-Phosphinoamidinato N-Heterocyclic Carbene-Diboravinyl Cation

T2 - Boron Analogue of Vinyl Cation

AU - Fan, Jun

AU - Chia, Pei Ting

AU - Zhang, Zheng Feng

AU - Yang, Ming Chung

AU - Su, Ming Der

AU - So, Cheuk Wai

PY - 2022/11/14

Y1 - 2022/11/14

N2 - A boron analogue of vinyl cation, pyridine-stabilized N-phosphinoamidinato N-heterocyclic carbene (NHC)-diboravinyl cation 2+, was synthesized by displacement of bromide in diborene 1 with excess pyridine. Experimental and computational studies showed that the positive charge is mainly at the B−B skeleton with delocalization to the pyridine ligand. One of the main modes of reactivity is through the B=B double bond alongside activation of the pyridine substituent, where the Bpyridine center is the predominant nucleophilic center and the predominant electrophilic center is either the activated pyridine para position or the BNHC center, illustrating the presence of diborene cation A, borylene-borenium cation B and diborene-pyridinium cation C resonance structures in cation 2+.

AB - A boron analogue of vinyl cation, pyridine-stabilized N-phosphinoamidinato N-heterocyclic carbene (NHC)-diboravinyl cation 2+, was synthesized by displacement of bromide in diborene 1 with excess pyridine. Experimental and computational studies showed that the positive charge is mainly at the B−B skeleton with delocalization to the pyridine ligand. One of the main modes of reactivity is through the B=B double bond alongside activation of the pyridine substituent, where the Bpyridine center is the predominant nucleophilic center and the predominant electrophilic center is either the activated pyridine para position or the BNHC center, illustrating the presence of diborene cation A, borylene-borenium cation B and diborene-pyridinium cation C resonance structures in cation 2+.

KW - Boron

KW - Diborene

KW - Small Molecule Activation

KW - Vinyl Cation

UR - http://www.scopus.com/inward/record.url?scp=85139931565&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85139931565&partnerID=8YFLogxK

U2 - 10.1002/anie.202212842

DO - 10.1002/anie.202212842

M3 - Article

AN - SCOPUS:85139931565

SN - 1433-7851

VL - 61

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 46

M1 - e202212842

ER -

A Pyridine-Stabilized N-Phosphinoamidinato N-Heterocyclic Carbene-Diboravinyl Cation: Boron Analogue of Vinyl Cation

Abstract

Bibliographical note

ASJC Scopus Subject Areas

Keywords

Access to Document

Other files and links

Fingerprint

Cite this