η 1 ‐Vinylidene to η 2 ‐Alkyne Isomerization of Tungsten and Molybdenum Complexes
The thermal isomerizations of η 1 ‐vinylidene complexes [(η 5 ‐C 5 H 5 )(CO)(NO)W=C=CHR] [ 5a , R = Si(CH 3 ) 2 C(CH 3 ) 3 ; 5c , R = C(CH 3 ) 3 ] as well as [(η 5 ‐C 5 H 5 )(CO)(NO)Mo=C=CHC(CH 3 ) 3 ] ( 8 ), to the corresponding η 2 ‐1‐alkyne complexes [(η 5 ‐C 5 H 5 )(CO)(NO)W(η 2 ‐H−C≡C−R)] [ 7a...
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| Veröffentlicht in: | European journal of inorganic chemistry 2003-12, Vol.2003 (24), p.4313-4320 |
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| container_title | European journal of inorganic chemistry |
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| creator | Ipaktschi, Junes Mohsseni‐Ala, Javad Uhlig, Sascha |
| description | The thermal isomerizations of η
1
‐vinylidene complexes [(η
5
‐C
5
H
5
)(CO)(NO)W=C=CHR] [
5a
, R = Si(CH
3
)
2
C(CH
3
)
3
;
5c
, R = C(CH
3
)
3
] as well as [(η
5
‐C
5
H
5
)(CO)(NO)Mo=C=CHC(CH
3
)
3
] (
8
), to the corresponding η
2
‐1‐alkyne complexes [(η
5
‐C
5
H
5
)(CO)(NO)W(η
2
‐H−C≡C−R)] [
7a
, R = Si(CH
3
)
2
C(CH
3
)
3
;
7c
, R = C(CH
3
)
3
] and [(η
5
‐C
5
H
5
)(CO)(NO)Mo{η
2
‐H−C≡C−CHC(CH
3
)
3
}] (
9
) has been investigated. Activation parameters for the isomerization of
5a
in [D
6
]benzene and
8
in [D
8
]toluene and [D
5
]ethanol were determined. In [D
8
]toluene η
1
‐vinylidene complex
5a
undergoes a single step 1,2‐shift of the silyl group from C
β
to C
α
. However, complex
8
shows dichotomous behavior. The isomerization
8
⇄
9
, dependent upon the solvent applied, occurs by means of two different pathways: in a nonpolar solvent,
8
tautomerizes via the 1,2‐migration of the hydrogen atom to
9
and in ethanol this tautomerization proceeds by a multi‐step process via deprotonation‐protonation and subsequent reductive elimination. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) |
| doi_str_mv | 10.1002/ejic.200300314 |
| format | Article |
| fullrecord | <record><control><sourceid>crossref</sourceid><recordid>TN_cdi_crossref_primary_10_1002_ejic_200300314</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>10_1002_ejic_200300314</sourcerecordid><originalsourceid>FETCH-LOGICAL-c844-45ee33bf24bf5efd798c1bf89ea350291cf28ccd4e239d2e4553901444d54c853</originalsourceid><addsrcrecordid>eNo9kEtKxEAQhhtRcBzduu4LJPajeuxeDsHHwIibQZch6VRLj0l6SGfAuPII3sZbzCE8iQmKUFDFR_3_4iPkkrOUMyaucOttKhiT43A4IjPOjEnYQovj8QYJCTegT8lZjFs2vcnFjDwfviin3x-fT74dal9hi7QPdKRiosv6dRjJKoYGO_9e9D60NDi62bcvsceWFm1FH0I9lGNy39AsNLsa3zCekxNX1BEv_vacbG5vNtl9sn68W2XLdWI1QAIKUcrSCSidQlddG2156bTBQiomDLdOaGsrQCFNJRCUkoZxAKgUWK3knKS_tbYLMXbo8l3nm6Ibcs7yyUo-Wcn_rcgfwCBYzw</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>η 1 ‐Vinylidene to η 2 ‐Alkyne Isomerization of Tungsten and Molybdenum Complexes</title><source>Access via Wiley Online Library</source><creator>Ipaktschi, Junes ; Mohsseni‐Ala, Javad ; Uhlig, Sascha</creator><creatorcontrib>Ipaktschi, Junes ; Mohsseni‐Ala, Javad ; Uhlig, Sascha</creatorcontrib><description>The thermal isomerizations of η
1
‐vinylidene complexes [(η
5
‐C
5
H
5
)(CO)(NO)W=C=CHR] [
5a
, R = Si(CH
3
)
2
C(CH
3
)
3
;
5c
, R = C(CH
3
)
3
] as well as [(η
5
‐C
5
H
5
)(CO)(NO)Mo=C=CHC(CH
3
)
3
] (
8
), to the corresponding η
2
‐1‐alkyne complexes [(η
5
‐C
5
H
5
)(CO)(NO)W(η
2
‐H−C≡C−R)] [
7a
, R = Si(CH
3
)
2
C(CH
3
)
3
;
7c
, R = C(CH
3
)
3
] and [(η
5
‐C
5
H
5
)(CO)(NO)Mo{η
2
‐H−C≡C−CHC(CH
3
)
3
}] (
9
) has been investigated. Activation parameters for the isomerization of
5a
in [D
6
]benzene and
8
in [D
8
]toluene and [D
5
]ethanol were determined. In [D
8
]toluene η
1
‐vinylidene complex
5a
undergoes a single step 1,2‐shift of the silyl group from C
β
to C
α
. However, complex
8
shows dichotomous behavior. The isomerization
8
⇄
9
, dependent upon the solvent applied, occurs by means of two different pathways: in a nonpolar solvent,
8
tautomerizes via the 1,2‐migration of the hydrogen atom to
9
and in ethanol this tautomerization proceeds by a multi‐step process via deprotonation‐protonation and subsequent reductive elimination. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)</description><identifier>ISSN: 1434-1948</identifier><identifier>EISSN: 1099-0682</identifier><identifier>DOI: 10.1002/ejic.200300314</identifier><language>eng</language><ispartof>European journal of inorganic chemistry, 2003-12, Vol.2003 (24), p.4313-4320</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c844-45ee33bf24bf5efd798c1bf89ea350291cf28ccd4e239d2e4553901444d54c853</citedby><cites>FETCH-LOGICAL-c844-45ee33bf24bf5efd798c1bf89ea350291cf28ccd4e239d2e4553901444d54c853</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids></links><search><creatorcontrib>Ipaktschi, Junes</creatorcontrib><creatorcontrib>Mohsseni‐Ala, Javad</creatorcontrib><creatorcontrib>Uhlig, Sascha</creatorcontrib><title>η 1 ‐Vinylidene to η 2 ‐Alkyne Isomerization of Tungsten and Molybdenum Complexes</title><title>European journal of inorganic chemistry</title><description>The thermal isomerizations of η
1
‐vinylidene complexes [(η
5
‐C
5
H
5
)(CO)(NO)W=C=CHR] [
5a
, R = Si(CH
3
)
2
C(CH
3
)
3
;
5c
, R = C(CH
3
)
3
] as well as [(η
5
‐C
5
H
5
)(CO)(NO)Mo=C=CHC(CH
3
)
3
] (
8
), to the corresponding η
2
‐1‐alkyne complexes [(η
5
‐C
5
H
5
)(CO)(NO)W(η
2
‐H−C≡C−R)] [
7a
, R = Si(CH
3
)
2
C(CH
3
)
3
;
7c
, R = C(CH
3
)
3
] and [(η
5
‐C
5
H
5
)(CO)(NO)Mo{η
2
‐H−C≡C−CHC(CH
3
)
3
}] (
9
) has been investigated. Activation parameters for the isomerization of
5a
in [D
6
]benzene and
8
in [D
8
]toluene and [D
5
]ethanol were determined. In [D
8
]toluene η
1
‐vinylidene complex
5a
undergoes a single step 1,2‐shift of the silyl group from C
β
to C
α
. However, complex
8
shows dichotomous behavior. The isomerization
8
⇄
9
, dependent upon the solvent applied, occurs by means of two different pathways: in a nonpolar solvent,
8
tautomerizes via the 1,2‐migration of the hydrogen atom to
9
and in ethanol this tautomerization proceeds by a multi‐step process via deprotonation‐protonation and subsequent reductive elimination. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)</description><issn>1434-1948</issn><issn>1099-0682</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2003</creationdate><recordtype>article</recordtype><recordid>eNo9kEtKxEAQhhtRcBzduu4LJPajeuxeDsHHwIibQZch6VRLj0l6SGfAuPII3sZbzCE8iQmKUFDFR_3_4iPkkrOUMyaucOttKhiT43A4IjPOjEnYQovj8QYJCTegT8lZjFs2vcnFjDwfviin3x-fT74dal9hi7QPdKRiosv6dRjJKoYGO_9e9D60NDi62bcvsceWFm1FH0I9lGNy39AsNLsa3zCekxNX1BEv_vacbG5vNtl9sn68W2XLdWI1QAIKUcrSCSidQlddG2156bTBQiomDLdOaGsrQCFNJRCUkoZxAKgUWK3knKS_tbYLMXbo8l3nm6Ibcs7yyUo-Wcn_rcgfwCBYzw</recordid><startdate>200312</startdate><enddate>200312</enddate><creator>Ipaktschi, Junes</creator><creator>Mohsseni‐Ala, Javad</creator><creator>Uhlig, Sascha</creator><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>200312</creationdate><title>η 1 ‐Vinylidene to η 2 ‐Alkyne Isomerization of Tungsten and Molybdenum Complexes</title><author>Ipaktschi, Junes ; Mohsseni‐Ala, Javad ; Uhlig, Sascha</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c844-45ee33bf24bf5efd798c1bf89ea350291cf28ccd4e239d2e4553901444d54c853</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2003</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Ipaktschi, Junes</creatorcontrib><creatorcontrib>Mohsseni‐Ala, Javad</creatorcontrib><creatorcontrib>Uhlig, Sascha</creatorcontrib><collection>CrossRef</collection><jtitle>European journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Ipaktschi, Junes</au><au>Mohsseni‐Ala, Javad</au><au>Uhlig, Sascha</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>η 1 ‐Vinylidene to η 2 ‐Alkyne Isomerization of Tungsten and Molybdenum Complexes</atitle><jtitle>European journal of inorganic chemistry</jtitle><date>2003-12</date><risdate>2003</risdate><volume>2003</volume><issue>24</issue><spage>4313</spage><epage>4320</epage><pages>4313-4320</pages><issn>1434-1948</issn><eissn>1099-0682</eissn><abstract>The thermal isomerizations of η
1
‐vinylidene complexes [(η
5
‐C
5
H
5
)(CO)(NO)W=C=CHR] [
5a
, R = Si(CH
3
)
2
C(CH
3
)
3
;
5c
, R = C(CH
3
)
3
] as well as [(η
5
‐C
5
H
5
)(CO)(NO)Mo=C=CHC(CH
3
)
3
] (
8
), to the corresponding η
2
‐1‐alkyne complexes [(η
5
‐C
5
H
5
)(CO)(NO)W(η
2
‐H−C≡C−R)] [
7a
, R = Si(CH
3
)
2
C(CH
3
)
3
;
7c
, R = C(CH
3
)
3
] and [(η
5
‐C
5
H
5
)(CO)(NO)Mo{η
2
‐H−C≡C−CHC(CH
3
)
3
}] (
9
) has been investigated. Activation parameters for the isomerization of
5a
in [D
6
]benzene and
8
in [D
8
]toluene and [D
5
]ethanol were determined. In [D
8
]toluene η
1
‐vinylidene complex
5a
undergoes a single step 1,2‐shift of the silyl group from C
β
to C
α
. However, complex
8
shows dichotomous behavior. The isomerization
8
⇄
9
, dependent upon the solvent applied, occurs by means of two different pathways: in a nonpolar solvent,
8
tautomerizes via the 1,2‐migration of the hydrogen atom to
9
and in ethanol this tautomerization proceeds by a multi‐step process via deprotonation‐protonation and subsequent reductive elimination. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)</abstract><doi>10.1002/ejic.200300314</doi><tpages>8</tpages></addata></record> |
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| language | eng |
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| source | Access via Wiley Online Library |
| title | η 1 ‐Vinylidene to η 2 ‐Alkyne Isomerization of Tungsten and Molybdenum Complexes |
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