schliessen

Filtern

 

Bibliotheken

Synergistic Effects of Lewis Bases and Substituents on the Electronic Structure and Reactivity of Boryl Radicals

Boryl radicals have the potential for the development of new molecular entities and for application in new radical reactions. However, the effects of the substituents and coordinating Lewis bases on the reactivity of boryl radicals are not fully understood. By using first‐principles methods, we inve... Full description

Journal Title: Chemistry – A European Journal 03 February 2014, Vol.20(6), pp.1630-1637
Main Author: Lu, Dongmei
Other Authors: Wu, Chao , Li, Pengfei
Format: Electronic Article Electronic Article
Language: English
Subjects:
ID: ISSN: 0947-6539 ; E-ISSN: 1521-3765 ; DOI: 10.1002/chem.201303705
Zum Text:
SendSend as email Add to Book BagAdd to Book Bag
Staff View
recordid: wj10.1002/chem.201303705
title: Synergistic Effects of Lewis Bases and Substituents on the Electronic Structure and Reactivity of Boryl Radicals
format: Article
creator:
  • Lu, Dongmei
  • Wu, Chao
  • Li, Pengfei
subjects:
  • Boron
  • Boryl Radicals
  • Lewis Bases
  • Spin Density
  • Substituent Effects
  • Synergistic Effects
ispartof: Chemistry – A European Journal, 03 February 2014, Vol.20(6), pp.1630-1637
description: Boryl radicals have the potential for the development of new molecular entities and for application in new radical reactions. However, the effects of the substituents and coordinating Lewis bases on the reactivity of boryl radicals are not fully understood. By using first‐principles methods, we investigated the spin‐density distribution and reactivity of a series of boryl radicals with various substituents and Lewis bases. The substituents, along with the Lewis bases, only affect the radical reactivity when an unpaired electron is in the boron p orbital, that is, for three‐coordinate radicals. We found evidence of synergistic effects between the substituents and the Lewis bases that can substantially broaden the tunability of the reactivity of the boryl radicals. Among Lewis bases, pyridine and imidazol‐2‐ylidene show a similar capacity for stabilization by delocalizing the spin density. Electron‐donating substituents, such as nitrogen, more efficiently stabilize boryl radicals than oxygen and carbon atoms. The reactivity of a boryl radical is always boron based, irrespective of the spin density on boron. of substituents and Lewis bases on the reactivity of boryl radicals with various topologies are examined (see figure). Two electron‐donating substituents in combination with a good σ‐donating and π‐accepting Lewis base stabilize boryl radicals much more efficiently than if only substituents or Lewis bases are used.
language: eng
source:
identifier: ISSN: 0947-6539 ; E-ISSN: 1521-3765 ; DOI: 10.1002/chem.201303705
fulltext: fulltext
issn:
  • 0947-6539
  • 09476539
  • 1521-3765
  • 15213765
url: Link


@attributes
ID4825246
RANK0.07
NO1
SEARCH_ENGINEprimo_central_multiple_fe
SEARCH_ENGINE_TYPEPrimo Central Search Engine
LOCALfalse
PrimoNMBib
record
control
sourcerecordid10.1002/chem.201303705
sourceidwj
recordidTN_wj10.1002/chem.201303705
sourcesystemOther
pqid1492722446
galeid357244619
display
typearticle
titleSynergistic Effects of Lewis Bases and Substituents on the Electronic Structure and Reactivity of Boryl Radicals
creatorLu, Dongmei ; Wu, Chao ; Li, Pengfei
ispartofChemistry – A European Journal, 03 February 2014, Vol.20(6), pp.1630-1637
identifier
subjectBoron ; Boryl Radicals ; Lewis Bases ; Spin Density ; Substituent Effects ; Synergistic Effects
descriptionBoryl radicals have the potential for the development of new molecular entities and for application in new radical reactions. However, the effects of the substituents and coordinating Lewis bases on the reactivity of boryl radicals are not fully understood. By using first‐principles methods, we investigated the spin‐density distribution and reactivity of a series of boryl radicals with various substituents and Lewis bases. The substituents, along with the Lewis bases, only affect the radical reactivity when an unpaired electron is in the boron p orbital, that is, for three‐coordinate radicals. We found evidence of synergistic effects between the substituents and the Lewis bases that can substantially broaden the tunability of the reactivity of the boryl radicals. Among Lewis bases, pyridine and imidazol‐2‐ylidene show a similar capacity for stabilization by delocalizing the spin density. Electron‐donating substituents, such as nitrogen, more efficiently stabilize boryl radicals than oxygen and carbon atoms. The reactivity of a boryl radical is always boron based, irrespective of the spin density on boron. of substituents and Lewis bases on the reactivity of boryl radicals with various topologies are examined (see figure). Two electron‐donating substituents in combination with a good σ‐donating and π‐accepting Lewis base stabilize boryl radicals much more efficiently than if only substituents or Lewis bases are used.
languageeng
source
version8
lds50peer_reviewed
links
openurl$$Topenurl_article
openurlfulltext$$Topenurlfull_article
search
creatorcontrib
0Lu, Dongmei
1Wu, Chao
2Li, Pengfei
titleSynergistic Effects of Lewis Bases and Substituents on the Electronic Structure and Reactivity of Boryl Radicals
descriptionBoryl radicals have the potential for the development of new molecular entities and for application in new radical reactions. However, the effects of the substituents and coordinating Lewis bases on the reactivity of boryl radicals are not fully understood. By using first‐principles methods, we investigated the spin‐density distribution and reactivity of a series of boryl radicals with various substituents and Lewis bases. The substituents, along with the Lewis bases, only affect the radical reactivity when an unpaired electron is in the boron p orbital, that is, for three‐coordinate radicals. We found evidence of synergistic effects between the substituents and the Lewis bases that can substantially broaden the tunability of the reactivity of the boryl radicals. Among Lewis bases, pyridine and imidazol‐2‐ylidene show a similar capacity for stabilization by delocalizing the spin density. Electron‐donating substituents, such as nitrogen, more efficiently stabilize boryl radicals than oxygen and carbon atoms. The reactivity of a boryl radical is always boron based, irrespective of the spin density on boron. of substituents and Lewis bases on the reactivity of boryl radicals with various topologies are examined (see figure). Two electron‐donating substituents in combination with a good σ‐donating and π‐accepting Lewis base stabilize boryl radicals much more efficiently than if only substituents or Lewis bases are used.
subject
0Boron
1Boryl Radicals
2Lewis Bases
3Spin Density
4Substituent Effects
5Synergistic Effects
general
0English
1WILEY‐VCH Verlag
210.1002/chem.201303705
3Wiley Online Library
sourceidwj
recordidwj10.1002/chem.201303705
issn
00947-6539
109476539
21521-3765
315213765
rsrctypearticle
creationdate2014
addtitle
0Chemistry – A European Journal
1Chem. Eur. J.
searchscope
0wj
1wiley
scope
0wj
1wiley
lsr30VSR-Enriched:[pages, pqid, galeid]
sort
titleSynergistic Effects of Lewis Bases and Substituents on the Electronic Structure and Reactivity of Boryl Radicals
authorLu, Dongmei ; Wu, Chao ; Li, Pengfei
creationdate20140203
facets
frbrgroupid8983926265629721384
frbrtype5
languageeng
creationdate2014
topic
0Boron
1Boryl Radicals
2Lewis Bases
3Spin Density
4Substituent Effects
5Synergistic Effects
collectionWiley Online Library
prefilterarticles
rsrctypearticles
creatorcontrib
0Lu, Dongmei
1Wu, Chao
2Li, Pengfei
jtitleChemistry – A European Journal
toplevelpeer_reviewed
delivery
delcategoryRemote Search Resource
fulltextfulltext
addata
aulast
0Lu
1Wu
2Li
aufirst
0Dongmei
1Chao
2Pengfei
au
0Lu, Dongmei
1Wu, Chao
2Li, Pengfei
atitleSynergistic Effects of Lewis Bases and Substituents on the Electronic Structure and Reactivity of Boryl Radicals
jtitleChemistry – A European Journal
risdate20140203
volume20
issue6
spage1630
epage1637
issn0947-6539
eissn1521-3765
genrearticle
ristypeJOUR
abstractBoryl radicals have the potential for the development of new molecular entities and for application in new radical reactions. However, the effects of the substituents and coordinating Lewis bases on the reactivity of boryl radicals are not fully understood. By using first‐principles methods, we investigated the spin‐density distribution and reactivity of a series of boryl radicals with various substituents and Lewis bases. The substituents, along with the Lewis bases, only affect the radical reactivity when an unpaired electron is in the boron p orbital, that is, for three‐coordinate radicals. We found evidence of synergistic effects between the substituents and the Lewis bases that can substantially broaden the tunability of the reactivity of the boryl radicals. Among Lewis bases, pyridine and imidazol‐2‐ylidene show a similar capacity for stabilization by delocalizing the spin density. Electron‐donating substituents, such as nitrogen, more efficiently stabilize boryl radicals than oxygen and carbon atoms. The reactivity of a boryl radical is always boron based, irrespective of the spin density on boron. of substituents and Lewis bases on the reactivity of boryl radicals with various topologies are examined (see figure). Two electron‐donating substituents in combination with a good σ‐donating and π‐accepting Lewis base stabilize boryl radicals much more efficiently than if only substituents or Lewis bases are used.
copWeinheim
pubWILEY‐VCH Verlag
doi10.1002/chem.201303705
pages1630-1637
date2014-02-03