N-arylammonio- and N-pyridinium-substituted derivatives of dodecahydro-closo-dodecaborate(2-)

Andrea Vöge; Enno Lork; Behice Şebnem Sesalan; Detlef Gabel

doi:10.1016/j.jorganchem.2008.12.053

N-arylammonio- and N-pyridinium-substituted derivatives of dodecahydro-closo-dodecaborate(2-)

Andrea Vöge^*
, Enno Lork
, Behice Şebnem Sesalan
, Detlef Gabel

^*Corresponding author for this work

Department of Chemistry

University of Bremen

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

20 Citations (Scopus)

Abstract

We report two methods for preparing N-arylammonio, N-pyridyl and N-arylamino dodecaborates: heating of the tetrabutylammonium salt of dodecahydro-closo-dodecaborate(2-) with aryl and pyridyl amines, or nucleophilic attack of [closo-B₁₂H₁₁NH₂]^2- on a strongly deactivated aromatic system. With aryl amines we obtained [1-closo-B₁₂H₁₁N(R¹)₂C₆H₅]^- (R¹ = H, CH₃). With 4-(dimethylamino)pyridine, [1-closo-(B₁₂H₁₁NC₅H₄)-4-N(CH₃)₂]^-, with a bond between the boron and the pyridinium nitrogen, was obtained. A presumable mechanism for this kind of reactions is reported. By nucleophilic substitution, two products, [1-closo-(B₁₂H₁₁NHC₆H₃)-3,4-(CN)₂]^2- and [1-closo-(B₁₂H₁₁NHC₆H₂)-2-(NO₂)-4,5-(CN)₂]^2-, were formed with 4-nitrophthalonitrile and 1-chloro-2,4-dinitrobenzene gave [1-closo-(B₁₂H₁₁NHC₆H₃)-2,4-(NO₂)₂]^2-. For [1-closo-B₁₂H₁₁N(CH₃)₂C₆H₅]^- and [1-closo-(B₁₂H₁₁NHC₆H₃)-2,4-(NO₂)₂]^2- single crystal X-ray structures were obtained.

Original language	English
Pages (from-to)	1698-1703
Number of pages	6
Journal	Journal of Organometallic Chemistry
Volume	694
Issue number	11
DOIs	https://doi.org/10.1016/j.jorganchem.2008.12.053
Publication status	Published - 1 May 2009

Keywords

Aromatic substitution
B-pyridinium
Dodecahydro-closo-dodecaborate
Hofmann elimination
Hydroamination

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10.1016/j.jorganchem.2008.12.053

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@article{b43c5ea23efe44199e2e727e1a760853,

title = "N-arylammonio- and N-pyridinium-substituted derivatives of dodecahydro-closo-dodecaborate(2-)",

abstract = "We report two methods for preparing N-arylammonio, N-pyridyl and N-arylamino dodecaborates: heating of the tetrabutylammonium salt of dodecahydro-closo-dodecaborate(2-) with aryl and pyridyl amines, or nucleophilic attack of [closo-B12H11NH2]2- on a strongly deactivated aromatic system. With aryl amines we obtained [1-closo-B12H11N(R1)2C6H5]- (R1 = H, CH3). With 4-(dimethylamino)pyridine, [1-closo-(B12H11NC5H4)-4-N(CH3)2]-, with a bond between the boron and the pyridinium nitrogen, was obtained. A presumable mechanism for this kind of reactions is reported. By nucleophilic substitution, two products, [1-closo-(B12H11NHC6H3)-3,4-(CN)2]2- and [1-closo-(B12H11NHC6H2)-2-(NO2)-4,5-(CN)2]2-, were formed with 4-nitrophthalonitrile and 1-chloro-2,4-dinitrobenzene gave [1-closo-(B12H11NHC6H3)-2,4-(NO2)2]2-. For [1-closo-B12H11N(CH3)2C6H5]- and [1-closo-(B12H11NHC6H3)-2,4-(NO2)2]2- single crystal X-ray structures were obtained.",

keywords = "Aromatic substitution, B-pyridinium, Dodecahydro-closo-dodecaborate, Hofmann elimination, Hydroamination",

author = "Andrea V{\"o}ge and Enno Lork and Sesalan, \{Behice {\c S}ebnem\} and Detlef Gabel",

year = "2009",

month = may,

day = "1",

doi = "10.1016/j.jorganchem.2008.12.053",

language = "English",

volume = "694",

pages = "1698--1703",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "11",

}

TY - JOUR

T1 - N-arylammonio- and N-pyridinium-substituted derivatives of dodecahydro-closo-dodecaborate(2-)

AU - Vöge, Andrea

AU - Lork, Enno

AU - Sesalan, Behice Şebnem

AU - Gabel, Detlef

PY - 2009/5/1

Y1 - 2009/5/1

N2 - We report two methods for preparing N-arylammonio, N-pyridyl and N-arylamino dodecaborates: heating of the tetrabutylammonium salt of dodecahydro-closo-dodecaborate(2-) with aryl and pyridyl amines, or nucleophilic attack of [closo-B12H11NH2]2- on a strongly deactivated aromatic system. With aryl amines we obtained [1-closo-B12H11N(R1)2C6H5]- (R1 = H, CH3). With 4-(dimethylamino)pyridine, [1-closo-(B12H11NC5H4)-4-N(CH3)2]-, with a bond between the boron and the pyridinium nitrogen, was obtained. A presumable mechanism for this kind of reactions is reported. By nucleophilic substitution, two products, [1-closo-(B12H11NHC6H3)-3,4-(CN)2]2- and [1-closo-(B12H11NHC6H2)-2-(NO2)-4,5-(CN)2]2-, were formed with 4-nitrophthalonitrile and 1-chloro-2,4-dinitrobenzene gave [1-closo-(B12H11NHC6H3)-2,4-(NO2)2]2-. For [1-closo-B12H11N(CH3)2C6H5]- and [1-closo-(B12H11NHC6H3)-2,4-(NO2)2]2- single crystal X-ray structures were obtained.

AB - We report two methods for preparing N-arylammonio, N-pyridyl and N-arylamino dodecaborates: heating of the tetrabutylammonium salt of dodecahydro-closo-dodecaborate(2-) with aryl and pyridyl amines, or nucleophilic attack of [closo-B12H11NH2]2- on a strongly deactivated aromatic system. With aryl amines we obtained [1-closo-B12H11N(R1)2C6H5]- (R1 = H, CH3). With 4-(dimethylamino)pyridine, [1-closo-(B12H11NC5H4)-4-N(CH3)2]-, with a bond between the boron and the pyridinium nitrogen, was obtained. A presumable mechanism for this kind of reactions is reported. By nucleophilic substitution, two products, [1-closo-(B12H11NHC6H3)-3,4-(CN)2]2- and [1-closo-(B12H11NHC6H2)-2-(NO2)-4,5-(CN)2]2-, were formed with 4-nitrophthalonitrile and 1-chloro-2,4-dinitrobenzene gave [1-closo-(B12H11NHC6H3)-2,4-(NO2)2]2-. For [1-closo-B12H11N(CH3)2C6H5]- and [1-closo-(B12H11NHC6H3)-2,4-(NO2)2]2- single crystal X-ray structures were obtained.

KW - Aromatic substitution

KW - B-pyridinium

KW - Dodecahydro-closo-dodecaborate

KW - Hofmann elimination

KW - Hydroamination

UR - https://www.scopus.com/pages/publications/63249132833

U2 - 10.1016/j.jorganchem.2008.12.053

DO - 10.1016/j.jorganchem.2008.12.053

M3 - Article

AN - SCOPUS:63249132833

SN - 0022-328X

VL - 694

SP - 1698

EP - 1703

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 11

ER -

N-arylammonio- and N-pyridinium-substituted derivatives of dodecahydro-closo-dodecaborate(2-)

Abstract

Keywords

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