New reactivity at the silicon bridge in sila[1]ferrocenophanes
We describe two new types of reactivity involving silicon-bridged [1]ferrocenophanes. In an attempt to form a [1]ferrocenophane with a bridging silyl cation, the reaction of sila[1]ferrocenophane [Fe(η-C 5 H 4 ) 2 Si(H)TMP] ( 12 ) (TMP = 2,2,6,6-tetramethylpiperidyl) towards the hydride-abstraction...
Gespeichert in:
| Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2018, Vol.47 (8), p.2759-2768 |
|---|---|
| Hauptverfasser: | , , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 2768 |
|---|---|
| container_issue | 8 |
| container_start_page | 2759 |
| container_title | Dalton transactions : an international journal of inorganic chemistry |
| container_volume | 47 |
| creator | Musgrave, Rebecca A Hailes, Rebekah L. N Schäfer, André Russell, Andrew D Gates, Paul J Manners, Ian |
| description | We describe two new types of reactivity involving silicon-bridged [1]ferrocenophanes. In an attempt to form a [1]ferrocenophane with a bridging silyl cation, the reaction of sila[1]ferrocenophane [Fe(η-C
5
H
4
)
2
Si(H)TMP] (
12
) (TMP = 2,2,6,6-tetramethylpiperidyl) towards the hydride-abstraction reagent trityl tetrakis(pentafluorophenyl)borate ([CPh
3
][B(C
6
F
5
)
4
]) was explored. This yielded the unusual dinuclear species [Fe(η-C
5
H
4
)
2
Si(TMP·H)(η-C
5
H
3
)Fe(η-C
5
H
4
)Si(H)TMP][B(C
6
F
5
)
4
]
[13][B(C
6
F
5
)
4
]
in low yield. The formation of
[13]
+
is proposed to involve abstraction of hydride from the silicon bridge in
12
with subsequent C-H bond cleavage of a cyclopentadienyl group by the resulting electrophilic transient silyl cation intermediate. We also explored the reaction of dimethylsila[1]ferrocenophane [Fe(η-C
5
H
4
)
2
SiMe
2
] (
1
) with the Au(
i
) species AuCl(PMe
3
). This was found to result in addition of the Au-Cl bond across the Cp
ipso
-Si bond to yield the ring-opened species [1′-(chlorodimethylsilyl)-ferrocenyl](trimethylphosphine)gold(
i
), [Fe(C
5
H
4
SiMe
2
Cl){C
5
H
4
Au(PMe
3
)}] (
14
). This represents the first example of ring-opening addition of a metallocenophane with a reagent possessing a transition metal-halogen bond.
Two new types of reactivity involving silicon-bridged [1]ferrocenophanes are described. |
| doi_str_mv | 10.1039/c7dt04593j |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_pubme</sourceid><recordid>TN_cdi_rsc_primary_c7dt04593j</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2010856025</sourcerecordid><originalsourceid>FETCH-LOGICAL-c439t-e2becd2b9b850b90ed4727200cfc87efb40791b53f3581e8ce96c1b8f29478e83</originalsourceid><addsrcrecordid>eNpd0c9LwzAUB_AgipvTi3el4EWE6kvSNslFkPmboZd5EilN-uoyunYmrbL_3s7NCZ4S8j48vnxDyCGFcwpcXRiRNxDFik-3SJ9GQoSK8Wh7c2dJj-x5PwVgDGK2S3pMRVRQmvTJ5RN-BQ4z09hP2yyCrAmaCQbeltbUVaCdzd8xsNXyJXulbwU6Vxus6vkkq9Dvk50iKz0erM8Bebm9GQ_vw9Hz3cPwahSaiKsmRKbR5EwrLWPQCjCPBBMMwBRGCix0BEJRHfOCx5KiNKgSQ7UsuqBCouQDcrraO3f1R4u-SWfWGyzLLkTd-pQqpRIhKBMdPflHp3Xrqi5dyoCCjBNgcafOVsq42nuHRTp3dpa5RUohXbaaDsX1-KfVxw4fr1e2eob5hv7W2IGjFXDebKZ_38K_AYXUeuk</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2010856025</pqid></control><display><type>article</type><title>New reactivity at the silicon bridge in sila[1]ferrocenophanes</title><source>Royal Society Of Chemistry Journals</source><source>Alma/SFX Local Collection</source><creator>Musgrave, Rebecca A ; Hailes, Rebekah L. N ; Schäfer, André ; Russell, Andrew D ; Gates, Paul J ; Manners, Ian</creator><creatorcontrib>Musgrave, Rebecca A ; Hailes, Rebekah L. N ; Schäfer, André ; Russell, Andrew D ; Gates, Paul J ; Manners, Ian</creatorcontrib><description>We describe two new types of reactivity involving silicon-bridged [1]ferrocenophanes. In an attempt to form a [1]ferrocenophane with a bridging silyl cation, the reaction of sila[1]ferrocenophane [Fe(η-C
5
H
4
)
2
Si(H)TMP] (
12
) (TMP = 2,2,6,6-tetramethylpiperidyl) towards the hydride-abstraction reagent trityl tetrakis(pentafluorophenyl)borate ([CPh
3
][B(C
6
F
5
)
4
]) was explored. This yielded the unusual dinuclear species [Fe(η-C
5
H
4
)
2
Si(TMP·H)(η-C
5
H
3
)Fe(η-C
5
H
4
)Si(H)TMP][B(C
6
F
5
)
4
]
[13][B(C
6
F
5
)
4
]
in low yield. The formation of
[13]
+
is proposed to involve abstraction of hydride from the silicon bridge in
12
with subsequent C-H bond cleavage of a cyclopentadienyl group by the resulting electrophilic transient silyl cation intermediate. We also explored the reaction of dimethylsila[1]ferrocenophane [Fe(η-C
5
H
4
)
2
SiMe
2
] (
1
) with the Au(
i
) species AuCl(PMe
3
). This was found to result in addition of the Au-Cl bond across the Cp
ipso
-Si bond to yield the ring-opened species [1′-(chlorodimethylsilyl)-ferrocenyl](trimethylphosphine)gold(
i
), [Fe(C
5
H
4
SiMe
2
Cl){C
5
H
4
Au(PMe
3
)}] (
14
). This represents the first example of ring-opening addition of a metallocenophane with a reagent possessing a transition metal-halogen bond.
Two new types of reactivity involving silicon-bridged [1]ferrocenophanes are described.</description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/c7dt04593j</identifier><identifier>PMID: 29417116</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Cations ; Ferrocenophanes ; Gold ; Hydrides ; Hydrogen bonds ; Silicon</subject><ispartof>Dalton transactions : an international journal of inorganic chemistry, 2018, Vol.47 (8), p.2759-2768</ispartof><rights>Copyright Royal Society of Chemistry 2018</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c439t-e2becd2b9b850b90ed4727200cfc87efb40791b53f3581e8ce96c1b8f29478e83</citedby><cites>FETCH-LOGICAL-c439t-e2becd2b9b850b90ed4727200cfc87efb40791b53f3581e8ce96c1b8f29478e83</cites><orcidid>0000-0002-5969-6618 ; 0000-0001-9404-0422 ; 0000-0001-8619-7745</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,4024,27923,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/29417116$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Musgrave, Rebecca A</creatorcontrib><creatorcontrib>Hailes, Rebekah L. N</creatorcontrib><creatorcontrib>Schäfer, André</creatorcontrib><creatorcontrib>Russell, Andrew D</creatorcontrib><creatorcontrib>Gates, Paul J</creatorcontrib><creatorcontrib>Manners, Ian</creatorcontrib><title>New reactivity at the silicon bridge in sila[1]ferrocenophanes</title><title>Dalton transactions : an international journal of inorganic chemistry</title><addtitle>Dalton Trans</addtitle><description>We describe two new types of reactivity involving silicon-bridged [1]ferrocenophanes. In an attempt to form a [1]ferrocenophane with a bridging silyl cation, the reaction of sila[1]ferrocenophane [Fe(η-C
5
H
4
)
2
Si(H)TMP] (
12
) (TMP = 2,2,6,6-tetramethylpiperidyl) towards the hydride-abstraction reagent trityl tetrakis(pentafluorophenyl)borate ([CPh
3
][B(C
6
F
5
)
4
]) was explored. This yielded the unusual dinuclear species [Fe(η-C
5
H
4
)
2
Si(TMP·H)(η-C
5
H
3
)Fe(η-C
5
H
4
)Si(H)TMP][B(C
6
F
5
)
4
]
[13][B(C
6
F
5
)
4
]
in low yield. The formation of
[13]
+
is proposed to involve abstraction of hydride from the silicon bridge in
12
with subsequent C-H bond cleavage of a cyclopentadienyl group by the resulting electrophilic transient silyl cation intermediate. We also explored the reaction of dimethylsila[1]ferrocenophane [Fe(η-C
5
H
4
)
2
SiMe
2
] (
1
) with the Au(
i
) species AuCl(PMe
3
). This was found to result in addition of the Au-Cl bond across the Cp
ipso
-Si bond to yield the ring-opened species [1′-(chlorodimethylsilyl)-ferrocenyl](trimethylphosphine)gold(
i
), [Fe(C
5
H
4
SiMe
2
Cl){C
5
H
4
Au(PMe
3
)}] (
14
). This represents the first example of ring-opening addition of a metallocenophane with a reagent possessing a transition metal-halogen bond.
Two new types of reactivity involving silicon-bridged [1]ferrocenophanes are described.</description><subject>Cations</subject><subject>Ferrocenophanes</subject><subject>Gold</subject><subject>Hydrides</subject><subject>Hydrogen bonds</subject><subject>Silicon</subject><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2018</creationdate><recordtype>article</recordtype><recordid>eNpd0c9LwzAUB_AgipvTi3el4EWE6kvSNslFkPmboZd5EilN-uoyunYmrbL_3s7NCZ4S8j48vnxDyCGFcwpcXRiRNxDFik-3SJ9GQoSK8Wh7c2dJj-x5PwVgDGK2S3pMRVRQmvTJ5RN-BQ4z09hP2yyCrAmaCQbeltbUVaCdzd8xsNXyJXulbwU6Vxus6vkkq9Dvk50iKz0erM8Bebm9GQ_vw9Hz3cPwahSaiKsmRKbR5EwrLWPQCjCPBBMMwBRGCix0BEJRHfOCx5KiNKgSQ7UsuqBCouQDcrraO3f1R4u-SWfWGyzLLkTd-pQqpRIhKBMdPflHp3Xrqi5dyoCCjBNgcafOVsq42nuHRTp3dpa5RUohXbaaDsX1-KfVxw4fr1e2eob5hv7W2IGjFXDebKZ_38K_AYXUeuk</recordid><startdate>2018</startdate><enddate>2018</enddate><creator>Musgrave, Rebecca A</creator><creator>Hailes, Rebekah L. N</creator><creator>Schäfer, André</creator><creator>Russell, Andrew D</creator><creator>Gates, Paul J</creator><creator>Manners, Ian</creator><general>Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-5969-6618</orcidid><orcidid>https://orcid.org/0000-0001-9404-0422</orcidid><orcidid>https://orcid.org/0000-0001-8619-7745</orcidid></search><sort><creationdate>2018</creationdate><title>New reactivity at the silicon bridge in sila[1]ferrocenophanes</title><author>Musgrave, Rebecca A ; Hailes, Rebekah L. N ; Schäfer, André ; Russell, Andrew D ; Gates, Paul J ; Manners, Ian</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c439t-e2becd2b9b850b90ed4727200cfc87efb40791b53f3581e8ce96c1b8f29478e83</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2018</creationdate><topic>Cations</topic><topic>Ferrocenophanes</topic><topic>Gold</topic><topic>Hydrides</topic><topic>Hydrogen bonds</topic><topic>Silicon</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Musgrave, Rebecca A</creatorcontrib><creatorcontrib>Hailes, Rebekah L. N</creatorcontrib><creatorcontrib>Schäfer, André</creatorcontrib><creatorcontrib>Russell, Andrew D</creatorcontrib><creatorcontrib>Gates, Paul J</creatorcontrib><creatorcontrib>Manners, Ian</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>MEDLINE - Academic</collection><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Musgrave, Rebecca A</au><au>Hailes, Rebekah L. N</au><au>Schäfer, André</au><au>Russell, Andrew D</au><au>Gates, Paul J</au><au>Manners, Ian</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>New reactivity at the silicon bridge in sila[1]ferrocenophanes</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><addtitle>Dalton Trans</addtitle><date>2018</date><risdate>2018</risdate><volume>47</volume><issue>8</issue><spage>2759</spage><epage>2768</epage><pages>2759-2768</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract>We describe two new types of reactivity involving silicon-bridged [1]ferrocenophanes. In an attempt to form a [1]ferrocenophane with a bridging silyl cation, the reaction of sila[1]ferrocenophane [Fe(η-C
5
H
4
)
2
Si(H)TMP] (
12
) (TMP = 2,2,6,6-tetramethylpiperidyl) towards the hydride-abstraction reagent trityl tetrakis(pentafluorophenyl)borate ([CPh
3
][B(C
6
F
5
)
4
]) was explored. This yielded the unusual dinuclear species [Fe(η-C
5
H
4
)
2
Si(TMP·H)(η-C
5
H
3
)Fe(η-C
5
H
4
)Si(H)TMP][B(C
6
F
5
)
4
]
[13][B(C
6
F
5
)
4
]
in low yield. The formation of
[13]
+
is proposed to involve abstraction of hydride from the silicon bridge in
12
with subsequent C-H bond cleavage of a cyclopentadienyl group by the resulting electrophilic transient silyl cation intermediate. We also explored the reaction of dimethylsila[1]ferrocenophane [Fe(η-C
5
H
4
)
2
SiMe
2
] (
1
) with the Au(
i
) species AuCl(PMe
3
). This was found to result in addition of the Au-Cl bond across the Cp
ipso
-Si bond to yield the ring-opened species [1′-(chlorodimethylsilyl)-ferrocenyl](trimethylphosphine)gold(
i
), [Fe(C
5
H
4
SiMe
2
Cl){C
5
H
4
Au(PMe
3
)}] (
14
). This represents the first example of ring-opening addition of a metallocenophane with a reagent possessing a transition metal-halogen bond.
Two new types of reactivity involving silicon-bridged [1]ferrocenophanes are described.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>29417116</pmid><doi>10.1039/c7dt04593j</doi><tpages>1</tpages><orcidid>https://orcid.org/0000-0002-5969-6618</orcidid><orcidid>https://orcid.org/0000-0001-9404-0422</orcidid><orcidid>https://orcid.org/0000-0001-8619-7745</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1477-9226 |
| ispartof | Dalton transactions : an international journal of inorganic chemistry, 2018, Vol.47 (8), p.2759-2768 |
| issn | 1477-9226 1477-9234 |
| language | eng |
| recordid | cdi_rsc_primary_c7dt04593j |
| source | Royal Society Of Chemistry Journals; Alma/SFX Local Collection |
| subjects | Cations Ferrocenophanes Gold Hydrides Hydrogen bonds Silicon |
| title | New reactivity at the silicon bridge in sila[1]ferrocenophanes |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-22T11%3A26%3A34IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_pubme&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=New%20reactivity%20at%20the%20silicon%20bridge%20in%20sila%5B1%5Dferrocenophanes&rft.jtitle=Dalton%20transactions%20:%20an%20international%20journal%20of%20inorganic%20chemistry&rft.au=Musgrave,%20Rebecca%20A&rft.date=2018&rft.volume=47&rft.issue=8&rft.spage=2759&rft.epage=2768&rft.pages=2759-2768&rft.issn=1477-9226&rft.eissn=1477-9234&rft_id=info:doi/10.1039/c7dt04593j&rft_dat=%3Cproquest_pubme%3E2010856025%3C/proquest_pubme%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=2010856025&rft_id=info:pmid/29417116&rfr_iscdi=true |