An Anionic, Chelating C(sp 3 )/NHC ligand from the Combination of an N‑heterobicyclic Carbene and Barbituric Heterocycle

The coordination chemistry of the anionic NHC 1 – based on an imidazo­[1,5- a ]­pyridin-3-ylidene (IPy) platform substituted at the C5 position by an anionic barbituric heterocycle was studied with d 6 (Ru­(II), Mn­(I)) and d 8 (Pd­(II), Rh­(I), Ir­(I), Au­(III)) transition-metal centers. While the...

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Main Authors: Idir Benaissa (6000965), Katarzyna Gajda (1726207), Laure Vendier (1347666), Noël Lugan (1737850), Anna Kajetanowicz (4046599), Karol Grela (1478173), Véronique Michelet (1413130), Vincent César (1554919), Stéphanie Bastin (1716577)
Format: Other Non-Article Part of Journal/Newspaper
Language:unknown
Published: 1753
Subjects:
)
IPY
Online Access:https://doi.org/10.1021/acs.organomet.1c00458.s001
id ftsmithonian:oai:figshare.com:article/16628878
record_format openpolar
spelling ftsmithonian:oai:figshare.com:article/16628878 2023-05-15T16:55:53+02:00 An Anionic, Chelating C(sp 3 )/NHC ligand from the Combination of an N‑heterobicyclic Carbene and Barbituric Heterocycle Idir Benaissa (6000965) Katarzyna Gajda (1726207) Laure Vendier (1347666) Noël Lugan (1737850) Anna Kajetanowicz (4046599) Karol Grela (1478173) Véronique Michelet (1413130) Vincent César (1554919) Stéphanie Bastin (1716577) 1753-01-01T00:00:00Z https://doi.org/10.1021/acs.organomet.1c00458.s001 unknown https://figshare.com/articles/journal_contribution/An_Anionic_Chelating_C_sp_sup_3_sup_NHC_ligand_from_the_Combination_of_an_N_heterobicyclic_Carbene_and_Barbituric_Heterocycle/16628878 doi:10.1021/acs.organomet.1c00458.s001 CC BY-NC 4.0 CC-BY-NC Biophysics Biochemistry Medicine Environmental Sciences not elsewhere classified Chemical Sciences not elsewhere classified Physical Sciences not elsewhere classified strong donating character stretching frequencies recorded low catalyst loadings kinetic gold ­( isolated upon crystallization imidazo ­[ 1 exhibited high activities carboxylic acid derivatives au ­( iii antecedent gold ­( ) ir ­( ru ­(< b rh ­(< b aucl ­(< b zwitterionic nhc precursor appropriate metal precursor 9 </ b lateral barbituric heterocycle malonic carbon atoms co </ sub 8 </ sup 6 </ sup 2 </ sub c ­( sp anionic barbituric heterocycle barbituric heterocycle malonic carbon p </ metal centers chelating c barbituric moiety anionic nhc primary alcohols platform substituted free carbene external oxidant dehydrogenative synthesis coordination chemistry chelating behavior c5 position >]­ pyridin 5 -< Text Journal contribution 1753 ftsmithonian https://doi.org/10.1021/acs.organomet.1c00458.s001 2021-12-20T02:07:21Z The coordination chemistry of the anionic NHC 1 – based on an imidazo­[1,5- a ]­pyridin-3-ylidene (IPy) platform substituted at the C5 position by an anionic barbituric heterocycle was studied with d 6 (Ru­(II), Mn­(I)) and d 8 (Pd­(II), Rh­(I), Ir­(I), Au­(III)) transition-metal centers. While the anionic barbituric heterocycle is planar in the zwitterionic NHC precursor 1 ·H, NMR spectroscopic analyses supplemented by X-ray diffraction studies evidenced the chelating behavior of ligand 1 – through the carbenic and the malonic carbon atoms in all of the complexes, resulting from a deformation of the lateral barbituric heterocycle. The complexes were obtained by reaction of the free carbene with the appropriate metal precursor, except for the Au­(III) complex 10 , which was obtained by oxidation of the antecedent gold­(I) complex [AuCl­( 1 )] − with PhICl 2 as an external oxidant. During the course of the process, the kinetic gold­(I) intermediate 9 resulting from the oxidation of the malonic carbon of the barbituric moiety was isolated upon crystallization from the reaction mixture. The ν CO stretching frequencies recorded for complex [Rh­( 1 )­(CO) 2 ] ( 5 ) demonstrated the strong donating character of the malonate-C­(sp 3 )/NHC ligand 1 – . The ruthenium complex [Ru­( 1 )­Cl­( p -cymene)] ( 11 ) was implemented as a precatalyst in the dehydrogenative synthesis of carboxylic acid derivatives from primary alcohols and exhibited high activities at low catalyst loadings (25–250 ppm) and a large tolerance toward functional groups. Other Non-Article Part of Journal/Newspaper IPY Unknown
institution Open Polar
collection Unknown
op_collection_id ftsmithonian
language unknown
topic Biophysics
Biochemistry
Medicine
Environmental Sciences not elsewhere classified
Chemical Sciences not elsewhere classified
Physical Sciences not elsewhere classified
strong donating character
stretching frequencies recorded
low catalyst loadings
kinetic gold ­(
isolated upon crystallization
imidazo ­[ 1
exhibited high activities
carboxylic acid derivatives
au ­( iii
antecedent gold ­(
)
ir ­(
ru ­(< b
rh ­(< b
aucl ­(< b
zwitterionic nhc precursor
appropriate metal precursor
9 </ b
lateral barbituric heterocycle
malonic carbon atoms
co </ sub
8 </ sup
6 </ sup
2 </ sub
c ­( sp
anionic barbituric heterocycle
barbituric heterocycle
malonic carbon
p </
metal centers
chelating c
barbituric moiety
anionic nhc
primary alcohols
platform substituted
free carbene
external oxidant
dehydrogenative synthesis
coordination chemistry
chelating behavior
c5 position
>]­ pyridin
5 -<
spellingShingle Biophysics
Biochemistry
Medicine
Environmental Sciences not elsewhere classified
Chemical Sciences not elsewhere classified
Physical Sciences not elsewhere classified
strong donating character
stretching frequencies recorded
low catalyst loadings
kinetic gold ­(
isolated upon crystallization
imidazo ­[ 1
exhibited high activities
carboxylic acid derivatives
au ­( iii
antecedent gold ­(
)
ir ­(
ru ­(< b
rh ­(< b
aucl ­(< b
zwitterionic nhc precursor
appropriate metal precursor
9 </ b
lateral barbituric heterocycle
malonic carbon atoms
co </ sub
8 </ sup
6 </ sup
2 </ sub
c ­( sp
anionic barbituric heterocycle
barbituric heterocycle
malonic carbon
p </
metal centers
chelating c
barbituric moiety
anionic nhc
primary alcohols
platform substituted
free carbene
external oxidant
dehydrogenative synthesis
coordination chemistry
chelating behavior
c5 position
>]­ pyridin
5 -<
Idir Benaissa (6000965)
Katarzyna Gajda (1726207)
Laure Vendier (1347666)
Noël Lugan (1737850)
Anna Kajetanowicz (4046599)
Karol Grela (1478173)
Véronique Michelet (1413130)
Vincent César (1554919)
Stéphanie Bastin (1716577)
An Anionic, Chelating C(sp 3 )/NHC ligand from the Combination of an N‑heterobicyclic Carbene and Barbituric Heterocycle
topic_facet Biophysics
Biochemistry
Medicine
Environmental Sciences not elsewhere classified
Chemical Sciences not elsewhere classified
Physical Sciences not elsewhere classified
strong donating character
stretching frequencies recorded
low catalyst loadings
kinetic gold ­(
isolated upon crystallization
imidazo ­[ 1
exhibited high activities
carboxylic acid derivatives
au ­( iii
antecedent gold ­(
)
ir ­(
ru ­(< b
rh ­(< b
aucl ­(< b
zwitterionic nhc precursor
appropriate metal precursor
9 </ b
lateral barbituric heterocycle
malonic carbon atoms
co </ sub
8 </ sup
6 </ sup
2 </ sub
c ­( sp
anionic barbituric heterocycle
barbituric heterocycle
malonic carbon
p </
metal centers
chelating c
barbituric moiety
anionic nhc
primary alcohols
platform substituted
free carbene
external oxidant
dehydrogenative synthesis
coordination chemistry
chelating behavior
c5 position
>]­ pyridin
5 -<
description The coordination chemistry of the anionic NHC 1 – based on an imidazo­[1,5- a ]­pyridin-3-ylidene (IPy) platform substituted at the C5 position by an anionic barbituric heterocycle was studied with d 6 (Ru­(II), Mn­(I)) and d 8 (Pd­(II), Rh­(I), Ir­(I), Au­(III)) transition-metal centers. While the anionic barbituric heterocycle is planar in the zwitterionic NHC precursor 1 ·H, NMR spectroscopic analyses supplemented by X-ray diffraction studies evidenced the chelating behavior of ligand 1 – through the carbenic and the malonic carbon atoms in all of the complexes, resulting from a deformation of the lateral barbituric heterocycle. The complexes were obtained by reaction of the free carbene with the appropriate metal precursor, except for the Au­(III) complex 10 , which was obtained by oxidation of the antecedent gold­(I) complex [AuCl­( 1 )] − with PhICl 2 as an external oxidant. During the course of the process, the kinetic gold­(I) intermediate 9 resulting from the oxidation of the malonic carbon of the barbituric moiety was isolated upon crystallization from the reaction mixture. The ν CO stretching frequencies recorded for complex [Rh­( 1 )­(CO) 2 ] ( 5 ) demonstrated the strong donating character of the malonate-C­(sp 3 )/NHC ligand 1 – . The ruthenium complex [Ru­( 1 )­Cl­( p -cymene)] ( 11 ) was implemented as a precatalyst in the dehydrogenative synthesis of carboxylic acid derivatives from primary alcohols and exhibited high activities at low catalyst loadings (25–250 ppm) and a large tolerance toward functional groups.
format Other Non-Article Part of Journal/Newspaper
author Idir Benaissa (6000965)
Katarzyna Gajda (1726207)
Laure Vendier (1347666)
Noël Lugan (1737850)
Anna Kajetanowicz (4046599)
Karol Grela (1478173)
Véronique Michelet (1413130)
Vincent César (1554919)
Stéphanie Bastin (1716577)
author_facet Idir Benaissa (6000965)
Katarzyna Gajda (1726207)
Laure Vendier (1347666)
Noël Lugan (1737850)
Anna Kajetanowicz (4046599)
Karol Grela (1478173)
Véronique Michelet (1413130)
Vincent César (1554919)
Stéphanie Bastin (1716577)
author_sort Idir Benaissa (6000965)
title An Anionic, Chelating C(sp 3 )/NHC ligand from the Combination of an N‑heterobicyclic Carbene and Barbituric Heterocycle
title_short An Anionic, Chelating C(sp 3 )/NHC ligand from the Combination of an N‑heterobicyclic Carbene and Barbituric Heterocycle
title_full An Anionic, Chelating C(sp 3 )/NHC ligand from the Combination of an N‑heterobicyclic Carbene and Barbituric Heterocycle
title_fullStr An Anionic, Chelating C(sp 3 )/NHC ligand from the Combination of an N‑heterobicyclic Carbene and Barbituric Heterocycle
title_full_unstemmed An Anionic, Chelating C(sp 3 )/NHC ligand from the Combination of an N‑heterobicyclic Carbene and Barbituric Heterocycle
title_sort anionic, chelating c(sp 3 )/nhc ligand from the combination of an n‑heterobicyclic carbene and barbituric heterocycle
publishDate 1753
url https://doi.org/10.1021/acs.organomet.1c00458.s001
genre IPY
genre_facet IPY
op_relation https://figshare.com/articles/journal_contribution/An_Anionic_Chelating_C_sp_sup_3_sup_NHC_ligand_from_the_Combination_of_an_N_heterobicyclic_Carbene_and_Barbituric_Heterocycle/16628878
doi:10.1021/acs.organomet.1c00458.s001
op_rights CC BY-NC 4.0
op_rightsnorm CC-BY-NC
op_doi https://doi.org/10.1021/acs.organomet.1c00458.s001
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