Isolation of a three-coordinate boron cation with a boron-sulfur double bond

Daniel Franz; Elisabeth Irran; Shigeyoshi Inoue

doi:10.1002/anie.201407809

Isolation of a three-coordinate boron cation with a boron-sulfur double bond

Daniel Franz, Elisabeth Irran, Shigeyoshi Inoue

Technische Universität Berlin

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

58 Scopus citations

Abstract

The reaction of the bulky bis(imidazolin-2-iminato) ligand precursor (1,2-(L^MesNH)_2-C₂H₄)[OTs] ₂ (1²⁺2[OTs] ^-; L^Mes=1,3-dimesityl imidazolin-2-ylidene, OTs=p-toluenesulfonate) with lithium borohydride yields the boronium dihydride cation (1,2-(L^MesN) _2-C₂H₄)BH₂ [OTs] (2⁺ [OTs] ^-). The boronium cation 2⁺ [OTs] ^- reacts with elemental sulfur to give the thioxoborane salt (1,2-(L^MesN)_2-C₂H₄)BS[OTs] (3⁺ [OTs] ^-). The hitherto unknown compounds 1²⁺2[OTs] ^-, 2⁺ [OTs] ^-, and 3⁺ [OTs] ^- were fully characterized by spectroscopic methods and single-crystal X-ray diffraction. Moreover, DFT calculations were carried out to elucidate the bonding situation in 2⁺ and 3⁺. The theoretical, as well as crystallographic studies reveal that 3⁺ is the first example for a stable cationic complex of three-coordinate boron that bears a B=S double bond.

Original language	English
Pages (from-to)	14264-14268
Number of pages	5
Journal	Angewandte Chemie International Edition in English
Volume	53
Issue number	51
DOIs	https://doi.org/10.1002/anie.201407809
State	Published - 15 Dec 2014
Externally published	Yes

Keywords

Boron
Cations
Hydrides
Multiple bonds
Sulfur

Access to Document

10.1002/anie.201407809

Cite this

@article{4c09de262f0e45058e685fee2fca7e54,

title = "Isolation of a three-coordinate boron cation with a boron-sulfur double bond",

abstract = "The reaction of the bulky bis(imidazolin-2-iminato) ligand precursor (1,2-(LMesNH)2-C2H4)[OTs] 2 (12+2[OTs] -; LMes=1,3-dimesityl imidazolin-2-ylidene, OTs=p-toluenesulfonate) with lithium borohydride yields the boronium dihydride cation (1,2-(LMesN) 2-C2H4)BH2 [OTs] (2+ [OTs] -). The boronium cation 2+ [OTs] - reacts with elemental sulfur to give the thioxoborane salt (1,2-(LMesN)2-C2H4)BS[OTs] (3+ [OTs] -). The hitherto unknown compounds 12+2[OTs] -, 2+ [OTs] -, and 3+ [OTs] - were fully characterized by spectroscopic methods and single-crystal X-ray diffraction. Moreover, DFT calculations were carried out to elucidate the bonding situation in 2+ and 3+. The theoretical, as well as crystallographic studies reveal that 3+ is the first example for a stable cationic complex of three-coordinate boron that bears a B=S double bond.",

keywords = "Boron, Cations, Hydrides, Multiple bonds, Sulfur",

author = "Daniel Franz and Elisabeth Irran and Shigeyoshi Inoue",

note = "Publisher Copyright: {\textcopyright} 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.",

year = "2014",

month = dec,

day = "15",

doi = "10.1002/anie.201407809",

language = "English",

volume = "53",

pages = "14264--14268",

journal = "Angewandte Chemie International Edition in English",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

number = "51",

}

TY - JOUR

T1 - Isolation of a three-coordinate boron cation with a boron-sulfur double bond

AU - Franz, Daniel

AU - Irran, Elisabeth

AU - Inoue, Shigeyoshi

PY - 2014/12/15

Y1 - 2014/12/15

N2 - The reaction of the bulky bis(imidazolin-2-iminato) ligand precursor (1,2-(LMesNH)2-C2H4)[OTs] 2 (12+2[OTs] -; LMes=1,3-dimesityl imidazolin-2-ylidene, OTs=p-toluenesulfonate) with lithium borohydride yields the boronium dihydride cation (1,2-(LMesN) 2-C2H4)BH2 [OTs] (2+ [OTs] -). The boronium cation 2+ [OTs] - reacts with elemental sulfur to give the thioxoborane salt (1,2-(LMesN)2-C2H4)BS[OTs] (3+ [OTs] -). The hitherto unknown compounds 12+2[OTs] -, 2+ [OTs] -, and 3+ [OTs] - were fully characterized by spectroscopic methods and single-crystal X-ray diffraction. Moreover, DFT calculations were carried out to elucidate the bonding situation in 2+ and 3+. The theoretical, as well as crystallographic studies reveal that 3+ is the first example for a stable cationic complex of three-coordinate boron that bears a B=S double bond.

AB - The reaction of the bulky bis(imidazolin-2-iminato) ligand precursor (1,2-(LMesNH)2-C2H4)[OTs] 2 (12+2[OTs] -; LMes=1,3-dimesityl imidazolin-2-ylidene, OTs=p-toluenesulfonate) with lithium borohydride yields the boronium dihydride cation (1,2-(LMesN) 2-C2H4)BH2 [OTs] (2+ [OTs] -). The boronium cation 2+ [OTs] - reacts with elemental sulfur to give the thioxoborane salt (1,2-(LMesN)2-C2H4)BS[OTs] (3+ [OTs] -). The hitherto unknown compounds 12+2[OTs] -, 2+ [OTs] -, and 3+ [OTs] - were fully characterized by spectroscopic methods and single-crystal X-ray diffraction. Moreover, DFT calculations were carried out to elucidate the bonding situation in 2+ and 3+. The theoretical, as well as crystallographic studies reveal that 3+ is the first example for a stable cationic complex of three-coordinate boron that bears a B=S double bond.

KW - Boron

KW - Cations

KW - Hydrides

KW - Multiple bonds

KW - Sulfur

UR - http://www.scopus.com/inward/record.url?scp=84917710837&partnerID=8YFLogxK

U2 - 10.1002/anie.201407809

DO - 10.1002/anie.201407809

M3 - Article

AN - SCOPUS:84917710837

SN - 1433-7851

VL - 53

SP - 14264

EP - 14268

JO - Angewandte Chemie International Edition in English

JF - Angewandte Chemie International Edition in English

IS - 51

ER -

Isolation of a three-coordinate boron cation with a boron-sulfur double bond

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Cite this