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Electronic structure and catalytic aspects of [Ru(tpm)(bqdi)(Cl/H2O)]n, tpm = tris(1-pyrazolyl)methane and bqdi = o-benzoquinonediimineElectronic supplementary information (ESI) available. CCDC 904797 and 904798. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2dt32402d
The diamagnetic complexes [Ru(tpm)(bqdi)(Cl)]ClO 4 ([ 1 ]ClO 4 ) (tpm = tris(1-pyrazolyl)methane, bqdi = o -benzoquinonediimine) and [Ru(tpm)(bqdi)(H 2 O)](ClO 4 ) 2 ([ 2 ](ClO 4 ) 2 ) have been synthesized. The valence state-sensitive bond distances of coordinated bqdi [C-N: 1.311(5)/1.322(5) Å in...
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| creator | Agarwala, Hemlata Ehret, Fabian Chowdhury, Abhishek Dutta Maji, Somnath Mobin, Shaikh M Kaim, Wolfgang Lahiri, Goutam Kumar |
| description | The diamagnetic complexes [Ru(tpm)(bqdi)(Cl)]ClO
4
([
1
]ClO
4
) (tpm = tris(1-pyrazolyl)methane, bqdi =
o
-benzoquinonediimine) and [Ru(tpm)(bqdi)(H
2
O)](ClO
4
)
2
([
2
](ClO
4
)
2
) have been synthesized. The valence state-sensitive bond distances of coordinated bqdi [C-N: 1.311(5)/1.322(5) Å in [
1
]ClO
4
; 1.316(7)/1.314(7) Å in molecule
A
and 1.315(6)/1.299(7) Å in molecule
B
of [
2
](ClO
4
)
2
] imply its fully oxidised quinonediimine (bqdi
0
) character. DFT calculations of
1
+
confirm the {Ru
II
-bqdi
0
}
versus
the antiferromagnetically coupled {Ru
III
-bqdi&z.rad;
−
} alternative. The
1
H NMR spectra of [
1
]ClO
4
in different solvents show variations in chemical shift positions of the NH (bqdi) and CH (tpm) proton resonances due to their different degrees of acidity in different solvents. In CH
3
CN/0.1 mol dm
−3
Et
4
NClO
4
, [
1
]ClO
4
undergoes one reversible Ru
II
Ru
III
oxidation and two reductions, the reversible first electron uptake being bqdi based (bqdi
0
/bqdi&z.rad;
−
). The electrogenerated paramagnetic species {Ru
III
-bqdi
0
}(
1
2+
) and {Ru
II
-Q&z.rad;
−
}(
1
) exhibit Ru
III
-type (
1
2+
: <
g
> = 2.211/Δ
g
= 0.580) and radical-type (
1
:
g
= 1.988) EPR signals, respectively, as is confirmed by calculated spin densities (Ru: 0.767 in
1
2+
, bqdi: 0.857 in
1
). The aqua complex [
2
](ClO
4
)
2
exhibits two one-electron oxidations at pH = 7, suggesting the formation of {Ru
IV
&z.dbd;O} species. The electronic spectral features of
1
n
(
n
= charge associated with the different redox states of the chloro complex: 2+, 1+, 0) in CH
3
CN and of
2
2+
in H
2
O have been interpreted based on the TD-DFT calculations. The application potential of the aqua complex
2
2+
as a pre-catalyst towards the epoxidation of olefins has been explored in the presence of the sacrificial oxidant PhI(OAc)
2
in CH
2
Cl
2
at 298 K, showing the desired selectivity with a wide variety of alkenes. DFT calculations based on styrene as the model substrate predict that the epoxidation reaction proceeds through a concerted transition state pathway.
Redox series including {Ru
II
(bqdi
0
)Cl/H
2
O}
n
+
, {Ru
III
(bqdi
0
)Cl}
2+
, {Ru
II
(bqdi&z.rad;
−
)Cl}
0
, {Ru
III
(bqdi
0
)OH}
2+
, {Ru
IV
(bqdi
0
)O}
2+
and the application of the aqua complex for a selective epoxidation process are reported. |
| doi_str_mv | 10.1039/c2dt32402d |
| format | article |
| fullrecord | <record><control><sourceid>rsc</sourceid><recordid>TN_cdi_rsc_primary_c2dt32402d</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>c2dt32402d</sourcerecordid><originalsourceid>FETCH-rsc_primary_c2dt32402d3</originalsourceid><addsrcrecordid>eNqFkMFLwzAUxqMoOKcX78Lz1oLd2rRaK3jqNrbTQL2JjKxJXSRNYpIK3V9v3MQJgp7e4-X3vu99QegsiQdJnBbDClOX4izGdB_1kizPowKn2cF3j6-P0LG1r3GMcXyFe3vZWLDKGSV5BdaZtnKtYUAkhYo4Ijrn58Rqz1hQNTzdt4HTTRgs3ygPg1IMp3gePstL8FO4A2e4DZJId4aslehE2DC3InKr-LnjGRUtmVyrt5ZLJRnlvOGS_Tyj1VqwhklHTAdc1so0xHElIRg_zEIg74QLshRsAGU5KqGIs7zINw6b9mYAE2XAs9scprM-iVAvhuiV16c-mJeFcjYBzym3YgbYzn_rB5YxGM1nt_D7b0_QYU2EZadftY_OJ-PHchoZWy204Y0_fLHD0z66-Ot9oWmd_qfxAcwll1s</addsrcrecordid><sourcetype>Enrichment Source</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Electronic structure and catalytic aspects of [Ru(tpm)(bqdi)(Cl/H2O)]n, tpm = tris(1-pyrazolyl)methane and bqdi = o-benzoquinonediimineElectronic supplementary information (ESI) available. CCDC 904797 and 904798. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2dt32402d</title><source>Royal Society of Chemistry</source><creator>Agarwala, Hemlata ; Ehret, Fabian ; Chowdhury, Abhishek Dutta ; Maji, Somnath ; Mobin, Shaikh M ; Kaim, Wolfgang ; Lahiri, Goutam Kumar</creator><creatorcontrib>Agarwala, Hemlata ; Ehret, Fabian ; Chowdhury, Abhishek Dutta ; Maji, Somnath ; Mobin, Shaikh M ; Kaim, Wolfgang ; Lahiri, Goutam Kumar</creatorcontrib><description><![CDATA[The diamagnetic complexes [Ru(tpm)(bqdi)(Cl)]ClO
4
([
1
]ClO
4
) (tpm = tris(1-pyrazolyl)methane, bqdi =
o
-benzoquinonediimine) and [Ru(tpm)(bqdi)(H
2
O)](ClO
4
)
2
([
2
](ClO
4
)
2
) have been synthesized. The valence state-sensitive bond distances of coordinated bqdi [C-N: 1.311(5)/1.322(5) Å in [
1
]ClO
4
; 1.316(7)/1.314(7) Å in molecule
A
and 1.315(6)/1.299(7) Å in molecule
B
of [
2
](ClO
4
)
2
] imply its fully oxidised quinonediimine (bqdi
0
) character. DFT calculations of
1
+
confirm the {Ru
II
-bqdi
0
}
versus
the antiferromagnetically coupled {Ru
III
-bqdi&z.rad;
−
} alternative. The
1
H NMR spectra of [
1
]ClO
4
in different solvents show variations in chemical shift positions of the NH (bqdi) and CH (tpm) proton resonances due to their different degrees of acidity in different solvents. In CH
3
CN/0.1 mol dm
−3
Et
4
NClO
4
, [
1
]ClO
4
undergoes one reversible Ru
II
Ru
III
oxidation and two reductions, the reversible first electron uptake being bqdi based (bqdi
0
/bqdi&z.rad;
−
). The electrogenerated paramagnetic species {Ru
III
-bqdi
0
}(
1
2+
) and {Ru
II
-Q&z.rad;
−
}(
1
) exhibit Ru
III
-type (
1
2+
: <
g
> = 2.211/Δ
g
= 0.580) and radical-type (
1
:
g
= 1.988) EPR signals, respectively, as is confirmed by calculated spin densities (Ru: 0.767 in
1
2+
, bqdi: 0.857 in
1
). The aqua complex [
2
](ClO
4
)
2
exhibits two one-electron oxidations at pH = 7, suggesting the formation of {Ru
IV
&z.dbd;O} species. The electronic spectral features of
1
n
(
n
= charge associated with the different redox states of the chloro complex: 2+, 1+, 0) in CH
3
CN and of
2
2+
in H
2
O have been interpreted based on the TD-DFT calculations. The application potential of the aqua complex
2
2+
as a pre-catalyst towards the epoxidation of olefins has been explored in the presence of the sacrificial oxidant PhI(OAc)
2
in CH
2
Cl
2
at 298 K, showing the desired selectivity with a wide variety of alkenes. DFT calculations based on styrene as the model substrate predict that the epoxidation reaction proceeds through a concerted transition state pathway.
Redox series including {Ru
II
(bqdi
0
)Cl/H
2
O}
n
+
, {Ru
III
(bqdi
0
)Cl}
2+
, {Ru
II
(bqdi&z.rad;
−
)Cl}
0
, {Ru
III
(bqdi
0
)OH}
2+
, {Ru
IV
(bqdi
0
)O}
2+
and the application of the aqua complex for a selective epoxidation process are reported.]]></description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/c2dt32402d</identifier><language>eng</language><creationdate>2013-02</creationdate><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail></links><search><creatorcontrib>Agarwala, Hemlata</creatorcontrib><creatorcontrib>Ehret, Fabian</creatorcontrib><creatorcontrib>Chowdhury, Abhishek Dutta</creatorcontrib><creatorcontrib>Maji, Somnath</creatorcontrib><creatorcontrib>Mobin, Shaikh M</creatorcontrib><creatorcontrib>Kaim, Wolfgang</creatorcontrib><creatorcontrib>Lahiri, Goutam Kumar</creatorcontrib><title>Electronic structure and catalytic aspects of [Ru(tpm)(bqdi)(Cl/H2O)]n, tpm = tris(1-pyrazolyl)methane and bqdi = o-benzoquinonediimineElectronic supplementary information (ESI) available. CCDC 904797 and 904798. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2dt32402d</title><description><![CDATA[The diamagnetic complexes [Ru(tpm)(bqdi)(Cl)]ClO
4
([
1
]ClO
4
) (tpm = tris(1-pyrazolyl)methane, bqdi =
o
-benzoquinonediimine) and [Ru(tpm)(bqdi)(H
2
O)](ClO
4
)
2
([
2
](ClO
4
)
2
) have been synthesized. The valence state-sensitive bond distances of coordinated bqdi [C-N: 1.311(5)/1.322(5) Å in [
1
]ClO
4
; 1.316(7)/1.314(7) Å in molecule
A
and 1.315(6)/1.299(7) Å in molecule
B
of [
2
](ClO
4
)
2
] imply its fully oxidised quinonediimine (bqdi
0
) character. DFT calculations of
1
+
confirm the {Ru
II
-bqdi
0
}
versus
the antiferromagnetically coupled {Ru
III
-bqdi&z.rad;
−
} alternative. The
1
H NMR spectra of [
1
]ClO
4
in different solvents show variations in chemical shift positions of the NH (bqdi) and CH (tpm) proton resonances due to their different degrees of acidity in different solvents. In CH
3
CN/0.1 mol dm
−3
Et
4
NClO
4
, [
1
]ClO
4
undergoes one reversible Ru
II
Ru
III
oxidation and two reductions, the reversible first electron uptake being bqdi based (bqdi
0
/bqdi&z.rad;
−
). The electrogenerated paramagnetic species {Ru
III
-bqdi
0
}(
1
2+
) and {Ru
II
-Q&z.rad;
−
}(
1
) exhibit Ru
III
-type (
1
2+
: <
g
> = 2.211/Δ
g
= 0.580) and radical-type (
1
:
g
= 1.988) EPR signals, respectively, as is confirmed by calculated spin densities (Ru: 0.767 in
1
2+
, bqdi: 0.857 in
1
). The aqua complex [
2
](ClO
4
)
2
exhibits two one-electron oxidations at pH = 7, suggesting the formation of {Ru
IV
&z.dbd;O} species. The electronic spectral features of
1
n
(
n
= charge associated with the different redox states of the chloro complex: 2+, 1+, 0) in CH
3
CN and of
2
2+
in H
2
O have been interpreted based on the TD-DFT calculations. The application potential of the aqua complex
2
2+
as a pre-catalyst towards the epoxidation of olefins has been explored in the presence of the sacrificial oxidant PhI(OAc)
2
in CH
2
Cl
2
at 298 K, showing the desired selectivity with a wide variety of alkenes. DFT calculations based on styrene as the model substrate predict that the epoxidation reaction proceeds through a concerted transition state pathway.
Redox series including {Ru
II
(bqdi
0
)Cl/H
2
O}
n
+
, {Ru
III
(bqdi
0
)Cl}
2+
, {Ru
II
(bqdi&z.rad;
−
)Cl}
0
, {Ru
III
(bqdi
0
)OH}
2+
, {Ru
IV
(bqdi
0
)O}
2+
and the application of the aqua complex for a selective epoxidation process are reported.]]></description><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2013</creationdate><recordtype>article</recordtype><sourceid/><recordid>eNqFkMFLwzAUxqMoOKcX78Lz1oLd2rRaK3jqNrbTQL2JjKxJXSRNYpIK3V9v3MQJgp7e4-X3vu99QegsiQdJnBbDClOX4izGdB_1kizPowKn2cF3j6-P0LG1r3GMcXyFe3vZWLDKGSV5BdaZtnKtYUAkhYo4Ijrn58Rqz1hQNTzdt4HTTRgs3ygPg1IMp3gePstL8FO4A2e4DZJId4aslehE2DC3InKr-LnjGRUtmVyrt5ZLJRnlvOGS_Tyj1VqwhklHTAdc1so0xHElIRg_zEIg74QLshRsAGU5KqGIs7zINw6b9mYAE2XAs9scprM-iVAvhuiV16c-mJeFcjYBzym3YgbYzn_rB5YxGM1nt_D7b0_QYU2EZadftY_OJ-PHchoZWy204Y0_fLHD0z66-Ot9oWmd_qfxAcwll1s</recordid><startdate>20130212</startdate><enddate>20130212</enddate><creator>Agarwala, Hemlata</creator><creator>Ehret, Fabian</creator><creator>Chowdhury, Abhishek Dutta</creator><creator>Maji, Somnath</creator><creator>Mobin, Shaikh M</creator><creator>Kaim, Wolfgang</creator><creator>Lahiri, Goutam Kumar</creator><scope/></search><sort><creationdate>20130212</creationdate><title>Electronic structure and catalytic aspects of [Ru(tpm)(bqdi)(Cl/H2O)]n, tpm = tris(1-pyrazolyl)methane and bqdi = o-benzoquinonediimineElectronic supplementary information (ESI) available. CCDC 904797 and 904798. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2dt32402d</title><author>Agarwala, Hemlata ; Ehret, Fabian ; Chowdhury, Abhishek Dutta ; Maji, Somnath ; Mobin, Shaikh M ; Kaim, Wolfgang ; Lahiri, Goutam Kumar</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-rsc_primary_c2dt32402d3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2013</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Agarwala, Hemlata</creatorcontrib><creatorcontrib>Ehret, Fabian</creatorcontrib><creatorcontrib>Chowdhury, Abhishek Dutta</creatorcontrib><creatorcontrib>Maji, Somnath</creatorcontrib><creatorcontrib>Mobin, Shaikh M</creatorcontrib><creatorcontrib>Kaim, Wolfgang</creatorcontrib><creatorcontrib>Lahiri, Goutam Kumar</creatorcontrib></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Agarwala, Hemlata</au><au>Ehret, Fabian</au><au>Chowdhury, Abhishek Dutta</au><au>Maji, Somnath</au><au>Mobin, Shaikh M</au><au>Kaim, Wolfgang</au><au>Lahiri, Goutam Kumar</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Electronic structure and catalytic aspects of [Ru(tpm)(bqdi)(Cl/H2O)]n, tpm = tris(1-pyrazolyl)methane and bqdi = o-benzoquinonediimineElectronic supplementary information (ESI) available. CCDC 904797 and 904798. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2dt32402d</atitle><date>2013-02-12</date><risdate>2013</risdate><volume>42</volume><issue>1</issue><spage>3721</spage><epage>3734</epage><pages>3721-3734</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract><![CDATA[The diamagnetic complexes [Ru(tpm)(bqdi)(Cl)]ClO
4
([
1
]ClO
4
) (tpm = tris(1-pyrazolyl)methane, bqdi =
o
-benzoquinonediimine) and [Ru(tpm)(bqdi)(H
2
O)](ClO
4
)
2
([
2
](ClO
4
)
2
) have been synthesized. The valence state-sensitive bond distances of coordinated bqdi [C-N: 1.311(5)/1.322(5) Å in [
1
]ClO
4
; 1.316(7)/1.314(7) Å in molecule
A
and 1.315(6)/1.299(7) Å in molecule
B
of [
2
](ClO
4
)
2
] imply its fully oxidised quinonediimine (bqdi
0
) character. DFT calculations of
1
+
confirm the {Ru
II
-bqdi
0
}
versus
the antiferromagnetically coupled {Ru
III
-bqdi&z.rad;
−
} alternative. The
1
H NMR spectra of [
1
]ClO
4
in different solvents show variations in chemical shift positions of the NH (bqdi) and CH (tpm) proton resonances due to their different degrees of acidity in different solvents. In CH
3
CN/0.1 mol dm
−3
Et
4
NClO
4
, [
1
]ClO
4
undergoes one reversible Ru
II
Ru
III
oxidation and two reductions, the reversible first electron uptake being bqdi based (bqdi
0
/bqdi&z.rad;
−
). The electrogenerated paramagnetic species {Ru
III
-bqdi
0
}(
1
2+
) and {Ru
II
-Q&z.rad;
−
}(
1
) exhibit Ru
III
-type (
1
2+
: <
g
> = 2.211/Δ
g
= 0.580) and radical-type (
1
:
g
= 1.988) EPR signals, respectively, as is confirmed by calculated spin densities (Ru: 0.767 in
1
2+
, bqdi: 0.857 in
1
). The aqua complex [
2
](ClO
4
)
2
exhibits two one-electron oxidations at pH = 7, suggesting the formation of {Ru
IV
&z.dbd;O} species. The electronic spectral features of
1
n
(
n
= charge associated with the different redox states of the chloro complex: 2+, 1+, 0) in CH
3
CN and of
2
2+
in H
2
O have been interpreted based on the TD-DFT calculations. The application potential of the aqua complex
2
2+
as a pre-catalyst towards the epoxidation of olefins has been explored in the presence of the sacrificial oxidant PhI(OAc)
2
in CH
2
Cl
2
at 298 K, showing the desired selectivity with a wide variety of alkenes. DFT calculations based on styrene as the model substrate predict that the epoxidation reaction proceeds through a concerted transition state pathway.
Redox series including {Ru
II
(bqdi
0
)Cl/H
2
O}
n
+
, {Ru
III
(bqdi
0
)Cl}
2+
, {Ru
II
(bqdi&z.rad;
−
)Cl}
0
, {Ru
III
(bqdi
0
)OH}
2+
, {Ru
IV
(bqdi
0
)O}
2+
and the application of the aqua complex for a selective epoxidation process are reported.]]></abstract><doi>10.1039/c2dt32402d</doi><tpages>14</tpages></addata></record> |
| fulltext | fulltext |
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| recordid | cdi_rsc_primary_c2dt32402d |
| source | Royal Society of Chemistry |
| title | Electronic structure and catalytic aspects of [Ru(tpm)(bqdi)(Cl/H2O)]n, tpm = tris(1-pyrazolyl)methane and bqdi = o-benzoquinonediimineElectronic supplementary information (ESI) available. CCDC 904797 and 904798. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2dt32402d |
| url | http://sfxeu10.hosted.exlibrisgroup.com/loughborough?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-03-06T18%3A58%3A15IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-rsc&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Electronic%20structure%20and%20catalytic%20aspects%20of%20%5BRu(tpm)(bqdi)(Cl/H2O)%5Dn,%20tpm%20=%20tris(1-pyrazolyl)methane%20and%20bqdi%20=%20o-benzoquinonediimineElectronic%20supplementary%20information%20(ESI)%20available.%20CCDC%20904797%20and%20904798.%20For%20ESI%20and%20crystallographic%20data%20in%20CIF%20or%20other%20electronic%20format%20see%20DOI:%2010.1039/c2dt32402d&rft.au=Agarwala,%20Hemlata&rft.date=2013-02-12&rft.volume=42&rft.issue=1&rft.spage=3721&rft.epage=3734&rft.pages=3721-3734&rft.issn=1477-9226&rft.eissn=1477-9234&rft_id=info:doi/10.1039/c2dt32402d&rft_dat=%3Crsc%3Ec2dt32402d%3C/rsc%3E%3Cgrp_id%3Ecdi_FETCH-rsc_primary_c2dt32402d3%3C/grp_id%3E%3Coa%3E%3C/oa%3E%3Curl%3E%3C/url%3E&rft_id=info:oai/&rft_id=info:pmid/&rfr_iscdi=true |