Loading…
Interplay between Nitrones and (Nitrile)Pd II Complexes: Cycloaddition vs. Complexation Followed by Cyclopalladation and Deoxygenation Reactions
The reaction between the nitrone p ‐MeC 6 H 4 CH=N(Me)O and trans ‐[PdCl 2 (RCN) 2 ] (R = Ph, Me) in the corresponding RCN (or of the nitrone in neat RCN in the presence of PdCl 2 ) proceeds at 45 °C (R = Ph) or reflux (R = Me) for 1 d and allows the isolation of the Δ 4 ‐1,2,4‐oxadiazoline complexe...
Saved in:
| Published in: | European journal of inorganic chemistry 2005-08, Vol.2005 (15), p.3042-3048 |
|---|---|
| Main Authors: | , , , , , , |
| Format: | Article |
| Language: | English |
| Citations: | Items that this one cites Items that cite this one |
| Online Access: | Get full text |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| cited_by | cdi_FETCH-LOGICAL-c169t-b9e1ebbd5e4370cc2cd86b82becfcb5ed0c2232b048ea9f1e0fe305eba0fc0eb3 |
|---|---|
| cites | cdi_FETCH-LOGICAL-c169t-b9e1ebbd5e4370cc2cd86b82becfcb5ed0c2232b048ea9f1e0fe305eba0fc0eb3 |
| container_end_page | 3048 |
| container_issue | 15 |
| container_start_page | 3042 |
| container_title | European journal of inorganic chemistry |
| container_volume | 2005 |
| creator | Bokach, Nadezhda A. Krokhin, Artem A. Nazarov, Alexey A. Kukushkin, Vadim Yu Haukka, Matti Fraústo da Silva, João J. R. Pombeiro, Armando J. L. |
| description | The reaction between the nitrone
p
‐MeC
6
H
4
CH=N(Me)O and
trans
‐[PdCl
2
(RCN)
2
] (R = Ph, Me) in the corresponding RCN (or of the nitrone in neat RCN in the presence of PdCl
2
) proceeds at 45 °C (R = Ph) or reflux (R = Me) for 1 d and allows the isolation of the Δ
4
‐1,2,4‐oxadiazoline complexes [PdCl
2
{N
a
=C(R)ON(Me)C
b
H(C
6
H
4
Me‐
p
)}
2
(N
a
–C
b
)] (R = Ph
1
; R = Me
2
) in ca. 50 and ca. 15 % yields, respectively. The reaction time can be drastically reduced by focused microwave irradiation of the reaction mixture. In CH
2
Cl
2
or acetone, this reaction proceeds in another direction to achieve the unstable nitrone complex [PdCl
2
{
O
N(Me)=CH(C
6
H
4
Me‐
p
)}
2
] (
3
), which was characterized by electrospray mass spectrometry, IR and
1
H NMR spectroscopy. Complex
3
is the first representative of (nitrone)Pd
II
compounds and is the key intermediate in at least two further reactions, i.e. cyclopalladation to give the dimeric complex [Pd
2
(μ‐Cl)
2
{
O
N(Me)=C(H)
C
6
H
3
Me‐
p
}
2
] (
5
; 30 % isolated yield) and deoxygenation of the nitrone to furnish the imine compound [PdCl
2
{N(Me)=CH(C
6
H
4
Me‐
p
)}
2
] (
4
). The palladium complexes
1
,
2
,
4
and
5
were characterized by C, H, and N analyses, FAB‐MS, IR,
1
H and
13
C{
1
H} spectroscopy, while
4
and
5
additionally by X‐ray crystallography. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) |
| doi_str_mv | 10.1002/ejic.200500124 |
| format | article |
| fullrecord | <record><control><sourceid>crossref</sourceid><recordid>TN_cdi_crossref_primary_10_1002_ejic_200500124</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>10_1002_ejic_200500124</sourcerecordid><originalsourceid>FETCH-LOGICAL-c169t-b9e1ebbd5e4370cc2cd86b82becfcb5ed0c2232b048ea9f1e0fe305eba0fc0eb3</originalsourceid><addsrcrecordid>eNo9kE9PhDAUxBujievq1XOPegBfW0DwZtBVko0ao2fSPw_DpktJS3T5Fn5kRdTTmzczmcOPkFMGMQPgF7hpdcwBUgDGkz2yYFAUEWQ53__WiUgiViT5ITkKYQMAAkS2IJ9VN6DvrRypwuEDsaMP7eBdh4HKztCz6Wstnj8ZWlW0dNve4g7DFS1HbZ00ph1a19H3EP-F8sdYOWvdBxqqxrnaS2ulmcNp-QbdbnzDbnaeUepJhGNy0Egb8OT3Lsnr6valvI_Wj3dVeb2ONMuKIVIFMlTKpJiIS9Caa5NnKucKdaNVigY054IrSHKURcMQGhSQopLQaEAlliSed7V3IXhs6t63W-nHmkE98awnnvU_T_EFoChuFg</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Interplay between Nitrones and (Nitrile)Pd II Complexes: Cycloaddition vs. Complexation Followed by Cyclopalladation and Deoxygenation Reactions</title><source>Wiley-Blackwell Read & Publish Collection</source><creator>Bokach, Nadezhda A. ; Krokhin, Artem A. ; Nazarov, Alexey A. ; Kukushkin, Vadim Yu ; Haukka, Matti ; Fraústo da Silva, João J. R. ; Pombeiro, Armando J. L.</creator><creatorcontrib>Bokach, Nadezhda A. ; Krokhin, Artem A. ; Nazarov, Alexey A. ; Kukushkin, Vadim Yu ; Haukka, Matti ; Fraústo da Silva, João J. R. ; Pombeiro, Armando J. L.</creatorcontrib><description>The reaction between the nitrone
p
‐MeC
6
H
4
CH=N(Me)O and
trans
‐[PdCl
2
(RCN)
2
] (R = Ph, Me) in the corresponding RCN (or of the nitrone in neat RCN in the presence of PdCl
2
) proceeds at 45 °C (R = Ph) or reflux (R = Me) for 1 d and allows the isolation of the Δ
4
‐1,2,4‐oxadiazoline complexes [PdCl
2
{N
a
=C(R)ON(Me)C
b
H(C
6
H
4
Me‐
p
)}
2
(N
a
–C
b
)] (R = Ph
1
; R = Me
2
) in ca. 50 and ca. 15 % yields, respectively. The reaction time can be drastically reduced by focused microwave irradiation of the reaction mixture. In CH
2
Cl
2
or acetone, this reaction proceeds in another direction to achieve the unstable nitrone complex [PdCl
2
{
O
N(Me)=CH(C
6
H
4
Me‐
p
)}
2
] (
3
), which was characterized by electrospray mass spectrometry, IR and
1
H NMR spectroscopy. Complex
3
is the first representative of (nitrone)Pd
II
compounds and is the key intermediate in at least two further reactions, i.e. cyclopalladation to give the dimeric complex [Pd
2
(μ‐Cl)
2
{
O
N(Me)=C(H)
C
6
H
3
Me‐
p
}
2
] (
5
; 30 % isolated yield) and deoxygenation of the nitrone to furnish the imine compound [PdCl
2
{N(Me)=CH(C
6
H
4
Me‐
p
)}
2
] (
4
). The palladium complexes
1
,
2
,
4
and
5
were characterized by C, H, and N analyses, FAB‐MS, IR,
1
H and
13
C{
1
H} spectroscopy, while
4
and
5
additionally by X‐ray crystallography. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)</description><identifier>ISSN: 1434-1948</identifier><identifier>EISSN: 1099-0682</identifier><identifier>DOI: 10.1002/ejic.200500124</identifier><language>eng</language><ispartof>European journal of inorganic chemistry, 2005-08, Vol.2005 (15), p.3042-3048</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c169t-b9e1ebbd5e4370cc2cd86b82becfcb5ed0c2232b048ea9f1e0fe305eba0fc0eb3</citedby><cites>FETCH-LOGICAL-c169t-b9e1ebbd5e4370cc2cd86b82becfcb5ed0c2232b048ea9f1e0fe305eba0fc0eb3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27900,27901</link.rule.ids></links><search><creatorcontrib>Bokach, Nadezhda A.</creatorcontrib><creatorcontrib>Krokhin, Artem A.</creatorcontrib><creatorcontrib>Nazarov, Alexey A.</creatorcontrib><creatorcontrib>Kukushkin, Vadim Yu</creatorcontrib><creatorcontrib>Haukka, Matti</creatorcontrib><creatorcontrib>Fraústo da Silva, João J. R.</creatorcontrib><creatorcontrib>Pombeiro, Armando J. L.</creatorcontrib><title>Interplay between Nitrones and (Nitrile)Pd II Complexes: Cycloaddition vs. Complexation Followed by Cyclopalladation and Deoxygenation Reactions</title><title>European journal of inorganic chemistry</title><description>The reaction between the nitrone
p
‐MeC
6
H
4
CH=N(Me)O and
trans
‐[PdCl
2
(RCN)
2
] (R = Ph, Me) in the corresponding RCN (or of the nitrone in neat RCN in the presence of PdCl
2
) proceeds at 45 °C (R = Ph) or reflux (R = Me) for 1 d and allows the isolation of the Δ
4
‐1,2,4‐oxadiazoline complexes [PdCl
2
{N
a
=C(R)ON(Me)C
b
H(C
6
H
4
Me‐
p
)}
2
(N
a
–C
b
)] (R = Ph
1
; R = Me
2
) in ca. 50 and ca. 15 % yields, respectively. The reaction time can be drastically reduced by focused microwave irradiation of the reaction mixture. In CH
2
Cl
2
or acetone, this reaction proceeds in another direction to achieve the unstable nitrone complex [PdCl
2
{
O
N(Me)=CH(C
6
H
4
Me‐
p
)}
2
] (
3
), which was characterized by electrospray mass spectrometry, IR and
1
H NMR spectroscopy. Complex
3
is the first representative of (nitrone)Pd
II
compounds and is the key intermediate in at least two further reactions, i.e. cyclopalladation to give the dimeric complex [Pd
2
(μ‐Cl)
2
{
O
N(Me)=C(H)
C
6
H
3
Me‐
p
}
2
] (
5
; 30 % isolated yield) and deoxygenation of the nitrone to furnish the imine compound [PdCl
2
{N(Me)=CH(C
6
H
4
Me‐
p
)}
2
] (
4
). The palladium complexes
1
,
2
,
4
and
5
were characterized by C, H, and N analyses, FAB‐MS, IR,
1
H and
13
C{
1
H} spectroscopy, while
4
and
5
additionally by X‐ray crystallography. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)</description><issn>1434-1948</issn><issn>1099-0682</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2005</creationdate><recordtype>article</recordtype><recordid>eNo9kE9PhDAUxBujievq1XOPegBfW0DwZtBVko0ao2fSPw_DpktJS3T5Fn5kRdTTmzczmcOPkFMGMQPgF7hpdcwBUgDGkz2yYFAUEWQ53__WiUgiViT5ITkKYQMAAkS2IJ9VN6DvrRypwuEDsaMP7eBdh4HKztCz6Wstnj8ZWlW0dNve4g7DFS1HbZ00ph1a19H3EP-F8sdYOWvdBxqqxrnaS2ulmcNp-QbdbnzDbnaeUepJhGNy0Egb8OT3Lsnr6valvI_Wj3dVeb2ONMuKIVIFMlTKpJiIS9Caa5NnKucKdaNVigY054IrSHKURcMQGhSQopLQaEAlliSed7V3IXhs6t63W-nHmkE98awnnvU_T_EFoChuFg</recordid><startdate>20050805</startdate><enddate>20050805</enddate><creator>Bokach, Nadezhda A.</creator><creator>Krokhin, Artem A.</creator><creator>Nazarov, Alexey A.</creator><creator>Kukushkin, Vadim Yu</creator><creator>Haukka, Matti</creator><creator>Fraústo da Silva, João J. R.</creator><creator>Pombeiro, Armando J. L.</creator><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>20050805</creationdate><title>Interplay between Nitrones and (Nitrile)Pd II Complexes: Cycloaddition vs. Complexation Followed by Cyclopalladation and Deoxygenation Reactions</title><author>Bokach, Nadezhda A. ; Krokhin, Artem A. ; Nazarov, Alexey A. ; Kukushkin, Vadim Yu ; Haukka, Matti ; Fraústo da Silva, João J. R. ; Pombeiro, Armando J. L.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c169t-b9e1ebbd5e4370cc2cd86b82becfcb5ed0c2232b048ea9f1e0fe305eba0fc0eb3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2005</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Bokach, Nadezhda A.</creatorcontrib><creatorcontrib>Krokhin, Artem A.</creatorcontrib><creatorcontrib>Nazarov, Alexey A.</creatorcontrib><creatorcontrib>Kukushkin, Vadim Yu</creatorcontrib><creatorcontrib>Haukka, Matti</creatorcontrib><creatorcontrib>Fraústo da Silva, João J. R.</creatorcontrib><creatorcontrib>Pombeiro, Armando J. L.</creatorcontrib><collection>CrossRef</collection><jtitle>European journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Bokach, Nadezhda A.</au><au>Krokhin, Artem A.</au><au>Nazarov, Alexey A.</au><au>Kukushkin, Vadim Yu</au><au>Haukka, Matti</au><au>Fraústo da Silva, João J. R.</au><au>Pombeiro, Armando J. L.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Interplay between Nitrones and (Nitrile)Pd II Complexes: Cycloaddition vs. Complexation Followed by Cyclopalladation and Deoxygenation Reactions</atitle><jtitle>European journal of inorganic chemistry</jtitle><date>2005-08-05</date><risdate>2005</risdate><volume>2005</volume><issue>15</issue><spage>3042</spage><epage>3048</epage><pages>3042-3048</pages><issn>1434-1948</issn><eissn>1099-0682</eissn><abstract>The reaction between the nitrone
p
‐MeC
6
H
4
CH=N(Me)O and
trans
‐[PdCl
2
(RCN)
2
] (R = Ph, Me) in the corresponding RCN (or of the nitrone in neat RCN in the presence of PdCl
2
) proceeds at 45 °C (R = Ph) or reflux (R = Me) for 1 d and allows the isolation of the Δ
4
‐1,2,4‐oxadiazoline complexes [PdCl
2
{N
a
=C(R)ON(Me)C
b
H(C
6
H
4
Me‐
p
)}
2
(N
a
–C
b
)] (R = Ph
1
; R = Me
2
) in ca. 50 and ca. 15 % yields, respectively. The reaction time can be drastically reduced by focused microwave irradiation of the reaction mixture. In CH
2
Cl
2
or acetone, this reaction proceeds in another direction to achieve the unstable nitrone complex [PdCl
2
{
O
N(Me)=CH(C
6
H
4
Me‐
p
)}
2
] (
3
), which was characterized by electrospray mass spectrometry, IR and
1
H NMR spectroscopy. Complex
3
is the first representative of (nitrone)Pd
II
compounds and is the key intermediate in at least two further reactions, i.e. cyclopalladation to give the dimeric complex [Pd
2
(μ‐Cl)
2
{
O
N(Me)=C(H)
C
6
H
3
Me‐
p
}
2
] (
5
; 30 % isolated yield) and deoxygenation of the nitrone to furnish the imine compound [PdCl
2
{N(Me)=CH(C
6
H
4
Me‐
p
)}
2
] (
4
). The palladium complexes
1
,
2
,
4
and
5
were characterized by C, H, and N analyses, FAB‐MS, IR,
1
H and
13
C{
1
H} spectroscopy, while
4
and
5
additionally by X‐ray crystallography. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)</abstract><doi>10.1002/ejic.200500124</doi><tpages>7</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1434-1948 |
| ispartof | European journal of inorganic chemistry, 2005-08, Vol.2005 (15), p.3042-3048 |
| issn | 1434-1948 1099-0682 |
| language | eng |
| recordid | cdi_crossref_primary_10_1002_ejic_200500124 |
| source | Wiley-Blackwell Read & Publish Collection |
| title | Interplay between Nitrones and (Nitrile)Pd II Complexes: Cycloaddition vs. Complexation Followed by Cyclopalladation and Deoxygenation Reactions |
| url | http://sfxeu10.hosted.exlibrisgroup.com/loughborough?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-02-24T17%3A00%3A58IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-crossref&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Interplay%20between%20Nitrones%20and%20(Nitrile)Pd%20II%20Complexes:%20Cycloaddition%20vs.%20Complexation%20Followed%20by%20Cyclopalladation%20and%20Deoxygenation%20Reactions&rft.jtitle=European%20journal%20of%20inorganic%20chemistry&rft.au=Bokach,%20Nadezhda%20A.&rft.date=2005-08-05&rft.volume=2005&rft.issue=15&rft.spage=3042&rft.epage=3048&rft.pages=3042-3048&rft.issn=1434-1948&rft.eissn=1099-0682&rft_id=info:doi/10.1002/ejic.200500124&rft_dat=%3Ccrossref%3E10_1002_ejic_200500124%3C/crossref%3E%3Cgrp_id%3Ecdi_FETCH-LOGICAL-c169t-b9e1ebbd5e4370cc2cd86b82becfcb5ed0c2232b048ea9f1e0fe305eba0fc0eb3%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 |