Zirconium arene triple-decker sandwich complexes: synthesis, electronic structure and bonding
Reduction of a permethylpentalene zirconium( iv ) chloride complex [η 8 -Pn*Zr(μ-Cl) 3/2 ] 2 (μ-Cl) 2 Li·THF x with KC 8 in benzene results in activation of the aromatic solvent to yield an "inverted sandwich" complex, [η 8 -Pn*Zr] 2 (μ-η 6 :η 6 -C 6 H 6 ) ( 1 ). The reactions in toluene,...
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| Veröffentlicht in: | Chemical communications (Cambridge, England) England), 2017-11, Vol.53 (88), p.1248-1251 |
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| creator | Kilpatrick, A. F. R Green, J. C Turner, Z. R Buffet, J.-C O'Hare, D |
| description | Reduction of a permethylpentalene zirconium(
iv
) chloride complex [η
8
-Pn*Zr(μ-Cl)
3/2
]
2
(μ-Cl)
2
Li·THF
x
with KC
8
in benzene results in activation of the aromatic solvent to yield an "inverted sandwich" complex, [η
8
-Pn*Zr]
2
(μ-η
6
:η
6
-C
6
H
6
) (
1
). The reactions in toluene, cumene,
o
-xylene and
m
-xylene also yield analogous solvent activated triple-decker sandwich complexes, which have been structurally characterised by single-crystal X-ray diffraction. Edge energies in the Zr K-edge XANES spectra are not distinguishable between
1
and formally Zr(
ii
) and Zr(
iv
) reference compounds, suggesting a broad edge structure. DFT calculations best describe the bonding in
1
as highly covalent with frontier molecular orbitals showing almost equal contributions from benzene and the Zr-permethylpentalene fragments.
Reduction of a permethylpentalene zirconium(
iv
) chloride complex [η
8
-Pn*Zr(μ-Cl)
3/2
]
2
(μ-Cl)
2
Li·THF
x
with KC
8
in benzene results in activation of the aromatic solvent to yield an "inverted sandwich" complex, [η
8
-Pn*Zr]
2
(μ-η
6
:η
6
-C
6
H
6
) (
1
). |
| doi_str_mv | 10.1039/c7cc07083g |
| format | Article |
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iv
) chloride complex [η
8
-Pn*Zr(μ-Cl)
3/2
]
2
(μ-Cl)
2
Li·THF
x
with KC
8
in benzene results in activation of the aromatic solvent to yield an "inverted sandwich" complex, [η
8
-Pn*Zr]
2
(μ-η
6
:η
6
-C
6
H
6
) (
1
). The reactions in toluene, cumene,
o
-xylene and
m
-xylene also yield analogous solvent activated triple-decker sandwich complexes, which have been structurally characterised by single-crystal X-ray diffraction. Edge energies in the Zr K-edge XANES spectra are not distinguishable between
1
and formally Zr(
ii
) and Zr(
iv
) reference compounds, suggesting a broad edge structure. DFT calculations best describe the bonding in
1
as highly covalent with frontier molecular orbitals showing almost equal contributions from benzene and the Zr-permethylpentalene fragments.
Reduction of a permethylpentalene zirconium(
iv
) chloride complex [η
8
-Pn*Zr(μ-Cl)
3/2
]
2
(μ-Cl)
2
Li·THF
x
with KC
8
in benzene results in activation of the aromatic solvent to yield an "inverted sandwich" complex, [η
8
-Pn*Zr]
2
(μ-η
6
:η
6
-C
6
H
6
) (
1
).</description><identifier>ISSN: 1359-7345</identifier><identifier>EISSN: 1364-548X</identifier><identifier>DOI: 10.1039/c7cc07083g</identifier><identifier>PMID: 29063098</identifier><language>eng</language><publisher>England</publisher><ispartof>Chemical communications (Cambridge, England), 2017-11, Vol.53 (88), p.1248-1251</ispartof><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c345t-641d4776d673fb73944ba0c8951523407fc68fdf518a9e78482012eac8283b5a3</citedby><cites>FETCH-LOGICAL-c345t-641d4776d673fb73944ba0c8951523407fc68fdf518a9e78482012eac8283b5a3</cites><orcidid>0000-0003-2044-9203 ; 0000-0001-8054-8751 ; 0000-0002-2108-2709 ; 0000-0003-2062-9546</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/29063098$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Kilpatrick, A. F. R</creatorcontrib><creatorcontrib>Green, J. C</creatorcontrib><creatorcontrib>Turner, Z. R</creatorcontrib><creatorcontrib>Buffet, J.-C</creatorcontrib><creatorcontrib>O'Hare, D</creatorcontrib><title>Zirconium arene triple-decker sandwich complexes: synthesis, electronic structure and bonding</title><title>Chemical communications (Cambridge, England)</title><addtitle>Chem Commun (Camb)</addtitle><description>Reduction of a permethylpentalene zirconium(
iv
) chloride complex [η
8
-Pn*Zr(μ-Cl)
3/2
]
2
(μ-Cl)
2
Li·THF
x
with KC
8
in benzene results in activation of the aromatic solvent to yield an "inverted sandwich" complex, [η
8
-Pn*Zr]
2
(μ-η
6
:η
6
-C
6
H
6
) (
1
). The reactions in toluene, cumene,
o
-xylene and
m
-xylene also yield analogous solvent activated triple-decker sandwich complexes, which have been structurally characterised by single-crystal X-ray diffraction. Edge energies in the Zr K-edge XANES spectra are not distinguishable between
1
and formally Zr(
ii
) and Zr(
iv
) reference compounds, suggesting a broad edge structure. DFT calculations best describe the bonding in
1
as highly covalent with frontier molecular orbitals showing almost equal contributions from benzene and the Zr-permethylpentalene fragments.
Reduction of a permethylpentalene zirconium(
iv
) chloride complex [η
8
-Pn*Zr(μ-Cl)
3/2
]
2
(μ-Cl)
2
Li·THF
x
with KC
8
in benzene results in activation of the aromatic solvent to yield an "inverted sandwich" complex, [η
8
-Pn*Zr]
2
(μ-η
6
:η
6
-C
6
H
6
) (
1
).</description><issn>1359-7345</issn><issn>1364-548X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2017</creationdate><recordtype>article</recordtype><recordid>eNpFkctLxDAQxoMouq5evCs5ilhNmqRJvEnxBQteFESQkk6nWu1jTVp0_3u7ro-5zDDzm4_hG0L2ODvhTNhT0ABMMyOe18iEi0RGSpqH9WWtbKSFVFtkO4RXNgZXZpNsxZYlglkzIU-PlYeurYaGOo8t0t5X8xqjAuENPQ2uLT4qeKHQNWP7E8MZDYu2f8FQhWOKNULvx3WgofcD9INHOq7QvGuLqn3eIRulqwPu_uQpub-8uEuvo9nt1U16PotgPK6PEskLqXVSJFqUuRZWytwxMFZxFQvJdAmJKYtSceMsaiNNzHiMDkxsRK6cmJLDle7cd-8Dhj5rqgBY167FbggZt0oxHSvLRvRohYLvQvBYZnNfNc4vMs6ypZ1ZqtP0286rET740R3yBos_9Ne_EdhfAT7A3_T_H-IL6Px6Xg</recordid><startdate>20171102</startdate><enddate>20171102</enddate><creator>Kilpatrick, A. F. R</creator><creator>Green, J. C</creator><creator>Turner, Z. R</creator><creator>Buffet, J.-C</creator><creator>O'Hare, D</creator><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0003-2044-9203</orcidid><orcidid>https://orcid.org/0000-0001-8054-8751</orcidid><orcidid>https://orcid.org/0000-0002-2108-2709</orcidid><orcidid>https://orcid.org/0000-0003-2062-9546</orcidid></search><sort><creationdate>20171102</creationdate><title>Zirconium arene triple-decker sandwich complexes: synthesis, electronic structure and bonding</title><author>Kilpatrick, A. F. R ; Green, J. C ; Turner, Z. R ; Buffet, J.-C ; O'Hare, D</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c345t-641d4776d673fb73944ba0c8951523407fc68fdf518a9e78482012eac8283b5a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2017</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kilpatrick, A. F. R</creatorcontrib><creatorcontrib>Green, J. C</creatorcontrib><creatorcontrib>Turner, Z. R</creatorcontrib><creatorcontrib>Buffet, J.-C</creatorcontrib><creatorcontrib>O'Hare, D</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Chemical communications (Cambridge, England)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kilpatrick, A. F. R</au><au>Green, J. C</au><au>Turner, Z. R</au><au>Buffet, J.-C</au><au>O'Hare, D</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Zirconium arene triple-decker sandwich complexes: synthesis, electronic structure and bonding</atitle><jtitle>Chemical communications (Cambridge, England)</jtitle><addtitle>Chem Commun (Camb)</addtitle><date>2017-11-02</date><risdate>2017</risdate><volume>53</volume><issue>88</issue><spage>1248</spage><epage>1251</epage><pages>1248-1251</pages><issn>1359-7345</issn><eissn>1364-548X</eissn><abstract>Reduction of a permethylpentalene zirconium(
iv
) chloride complex [η
8
-Pn*Zr(μ-Cl)
3/2
]
2
(μ-Cl)
2
Li·THF
x
with KC
8
in benzene results in activation of the aromatic solvent to yield an "inverted sandwich" complex, [η
8
-Pn*Zr]
2
(μ-η
6
:η
6
-C
6
H
6
) (
1
). The reactions in toluene, cumene,
o
-xylene and
m
-xylene also yield analogous solvent activated triple-decker sandwich complexes, which have been structurally characterised by single-crystal X-ray diffraction. Edge energies in the Zr K-edge XANES spectra are not distinguishable between
1
and formally Zr(
ii
) and Zr(
iv
) reference compounds, suggesting a broad edge structure. DFT calculations best describe the bonding in
1
as highly covalent with frontier molecular orbitals showing almost equal contributions from benzene and the Zr-permethylpentalene fragments.
Reduction of a permethylpentalene zirconium(
iv
) chloride complex [η
8
-Pn*Zr(μ-Cl)
3/2
]
2
(μ-Cl)
2
Li·THF
x
with KC
8
in benzene results in activation of the aromatic solvent to yield an "inverted sandwich" complex, [η
8
-Pn*Zr]
2
(μ-η
6
:η
6
-C
6
H
6
) (
1
).</abstract><cop>England</cop><pmid>29063098</pmid><doi>10.1039/c7cc07083g</doi><tpages>4</tpages><orcidid>https://orcid.org/0000-0003-2044-9203</orcidid><orcidid>https://orcid.org/0000-0001-8054-8751</orcidid><orcidid>https://orcid.org/0000-0002-2108-2709</orcidid><orcidid>https://orcid.org/0000-0003-2062-9546</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1359-7345 |
| ispartof | Chemical communications (Cambridge, England), 2017-11, Vol.53 (88), p.1248-1251 |
| issn | 1359-7345 1364-548X |
| language | eng |
| recordid | cdi_rsc_primary_c7cc07083g |
| source | Royal Society Of Chemistry Journals; Alma/SFX Local Collection |
| title | Zirconium arene triple-decker sandwich complexes: synthesis, electronic structure and bonding |
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