Isomers in chlorido and alkoxido-substituted oxidorhenium() complexes: effects on catalytic epoxidation activity
The syntheses and characterizations of oxidorhenium( v ) complexes trans -dichlorido [ReOCl 2 (PPh 3 )( L1a )] ( trans - 2a ), cis -dichlorido [ReOCl 2 (PPh 3 )( L1b )] ( cis - 2b ) and ethoxido-complex [ReO(OEt)( L1b ) 2 ] ( 4b ), ligated with the dimethyloxazoline-phenol ligands H L1a and H L1b ar...
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| Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2020-08, Vol.49 (32), p.11142-11149 |
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| creator | Schachner, Jörg A Belaj, Ferdinand Mösch-Zanetti, Nadia C |
| description | The syntheses and characterizations of oxidorhenium(
v
) complexes
trans
-dichlorido [ReOCl
2
(PPh
3
)(
L1a
)] (
trans
-
2a
),
cis
-dichlorido [ReOCl
2
(PPh
3
)(
L1b
)] (
cis
-
2b
) and ethoxido-complex [ReO(OEt)(
L1b
)
2
] (
4b
), ligated with the dimethyloxazoline-phenol ligands H
L1a
and H
L1b
are described. The bidentate ligand H
L1a
(2-(4,4-dimethyl-4,5-dihydro-1,3-oxazol-2-yl)-phenol) is unsubstituted on the phenol ring; ligand H
L1b
(2-(4,4-dimethyl-4,5-dihydro-1,3-oxazol-2-yl)-4-nitrophenol) contains a nitro group in
para
-position to the hydroxy group. In the reaction of precursor complex [ReOCl
3
(PPh
3
)
2
] and H
L1a
the two stereoisomers
cis
/
trans
-
2a
, with respect to chlorido ligands, are formed. The solid state structures of both isomers
cis
- and
trans
-
2a
were determined by single crystal X-ray diffraction analysis. In contrast, with ligand H
L1b
, only the
cis
-isomer
cis
-
2b
was obtained. Ethoxido-complex
4b
is exclusively obtained when precursor [ReOCl
3
(OPPh
3
)(SMe
2
)] is reacted with 2 equiv. of H
L1b
in ethanol in the presence of the base 2,6-dimethylpyridine (lutidine). If no lutidine is added, chlorido-complex [ReOCl(
L1b
)
2
] (
3b
) is obtained. Complexes [ReOCl
2
(PPh
3
)(
L1a
)] (
cis
/
trans
-
2a
), [ReOCl
2
(PPh
3
)(
L1b
)] (
cis
-
2b
), [ReO(OMe)(
L1a
)
2
] (
4a
) and [ReO(OEt)(
L1b
)
2
] (
4b
) were tested as homogeneous catalysts in the benchmark reaction of cyclooctene epoxidation. The influence of isomerism and effects of ligand substitutions on catalytic activity was investigated. Based on the time-conversion plots it can be concluded that
cis
/
trans
-isomerism does not influence catalytic activity, but electron-withdrawing substituents, as in
cis
-
2b
,
3b
and
4b
, show a beneficial effect.
Pairs of stereoisomers and chlorido/alkoxido oxidorhenium(
v
) complexes are described and allow for a systematic investigation of the influence on catalytic activity in standard cyclooctene epoxidation. |
| doi_str_mv | 10.1039/d0dt02352c |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_rsc_p</sourceid><recordid>TN_cdi_proquest_journals_2434704148</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2430093166</sourcerecordid><originalsourceid>FETCH-LOGICAL-c376t-c4c1ee64954ee934cce80ff83325ce76b70d56854ef6e822c158eb17c74636053</originalsourceid><addsrcrecordid>eNp90UtLxDAQAOAiCj4v3oWIl1Wo5tW09Sbra0HwoueSnU4x2jY1SWX335t1RcGDp2Qm3wzDJEkOGT1nVJQXNa0D5SLjsJHsMJnnacmF3Py5c7Wd7Hr_SinnNOM7yTDztkPniekJvLTWmdoS3ddEt292EYPUj3MfTBgD1uQr416wN2M3OSVgu6HFBfpLgk2DEDyxsY0Oul0GAwSHVYEOJmY1BPNhwnI_2Wp06_Hg-9xLnm9vnqb36cPj3Wx69ZCCyFVIQQJDVLLMJGIpJAAWtGkKIXgGmKt5TutMFfG1UVhwDiwrcM5yyKUSimZiL5ms-w7Ovo_oQ9UZD9i2ukc7-opLQWkpmFKRnvyhr3Z0fZxupWROJZNFVGdrBc5677CpBmc67ZYVo9Vq-dU1vX76Wv404uM1dh5-3O_nVEPdRHP0nxGfQ_CNoA</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2434704148</pqid></control><display><type>article</type><title>Isomers in chlorido and alkoxido-substituted oxidorhenium() complexes: effects on catalytic epoxidation activity</title><source>Royal Society Of Chemistry Journals 2008-</source><source>Alma/SFX Local Collection</source><creator>Schachner, Jörg A ; Belaj, Ferdinand ; Mösch-Zanetti, Nadia C</creator><creatorcontrib>Schachner, Jörg A ; Belaj, Ferdinand ; Mösch-Zanetti, Nadia C</creatorcontrib><description>The syntheses and characterizations of oxidorhenium(
v
) complexes
trans
-dichlorido [ReOCl
2
(PPh
3
)(
L1a
)] (
trans
-
2a
),
cis
-dichlorido [ReOCl
2
(PPh
3
)(
L1b
)] (
cis
-
2b
) and ethoxido-complex [ReO(OEt)(
L1b
)
2
] (
4b
), ligated with the dimethyloxazoline-phenol ligands H
L1a
and H
L1b
are described. The bidentate ligand H
L1a
(2-(4,4-dimethyl-4,5-dihydro-1,3-oxazol-2-yl)-phenol) is unsubstituted on the phenol ring; ligand H
L1b
(2-(4,4-dimethyl-4,5-dihydro-1,3-oxazol-2-yl)-4-nitrophenol) contains a nitro group in
para
-position to the hydroxy group. In the reaction of precursor complex [ReOCl
3
(PPh
3
)
2
] and H
L1a
the two stereoisomers
cis
/
trans
-
2a
, with respect to chlorido ligands, are formed. The solid state structures of both isomers
cis
- and
trans
-
2a
were determined by single crystal X-ray diffraction analysis. In contrast, with ligand H
L1b
, only the
cis
-isomer
cis
-
2b
was obtained. Ethoxido-complex
4b
is exclusively obtained when precursor [ReOCl
3
(OPPh
3
)(SMe
2
)] is reacted with 2 equiv. of H
L1b
in ethanol in the presence of the base 2,6-dimethylpyridine (lutidine). If no lutidine is added, chlorido-complex [ReOCl(
L1b
)
2
] (
3b
) is obtained. Complexes [ReOCl
2
(PPh
3
)(
L1a
)] (
cis
/
trans
-
2a
), [ReOCl
2
(PPh
3
)(
L1b
)] (
cis
-
2b
), [ReO(OMe)(
L1a
)
2
] (
4a
) and [ReO(OEt)(
L1b
)
2
] (
4b
) were tested as homogeneous catalysts in the benchmark reaction of cyclooctene epoxidation. The influence of isomerism and effects of ligand substitutions on catalytic activity was investigated. Based on the time-conversion plots it can be concluded that
cis
/
trans
-isomerism does not influence catalytic activity, but electron-withdrawing substituents, as in
cis
-
2b
,
3b
and
4b
, show a beneficial effect.
Pairs of stereoisomers and chlorido/alkoxido oxidorhenium(
v
) complexes are described and allow for a systematic investigation of the influence on catalytic activity in standard cyclooctene epoxidation.</description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/d0dt02352c</identifier><language>eng</language><publisher>Cambridge: Royal Society of Chemistry</publisher><subject>Catalytic activity ; Catalytic converters ; Crystallography ; Epoxidation ; Ethanol ; Isomers ; Ligands ; Nitrophenol ; NMR ; Nuclear magnetic resonance ; Phenols ; Precursors ; Single crystals ; Stereoisomerism</subject><ispartof>Dalton transactions : an international journal of inorganic chemistry, 2020-08, Vol.49 (32), p.11142-11149</ispartof><rights>Copyright Royal Society of Chemistry 2020</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c376t-c4c1ee64954ee934cce80ff83325ce76b70d56854ef6e822c158eb17c74636053</citedby><cites>FETCH-LOGICAL-c376t-c4c1ee64954ee934cce80ff83325ce76b70d56854ef6e822c158eb17c74636053</cites><orcidid>0000-0001-9749-2109 ; 0000-0002-1349-6725 ; 0000-0002-1863-4680</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27901,27902</link.rule.ids></links><search><creatorcontrib>Schachner, Jörg A</creatorcontrib><creatorcontrib>Belaj, Ferdinand</creatorcontrib><creatorcontrib>Mösch-Zanetti, Nadia C</creatorcontrib><title>Isomers in chlorido and alkoxido-substituted oxidorhenium() complexes: effects on catalytic epoxidation activity</title><title>Dalton transactions : an international journal of inorganic chemistry</title><description>The syntheses and characterizations of oxidorhenium(
v
) complexes
trans
-dichlorido [ReOCl
2
(PPh
3
)(
L1a
)] (
trans
-
2a
),
cis
-dichlorido [ReOCl
2
(PPh
3
)(
L1b
)] (
cis
-
2b
) and ethoxido-complex [ReO(OEt)(
L1b
)
2
] (
4b
), ligated with the dimethyloxazoline-phenol ligands H
L1a
and H
L1b
are described. The bidentate ligand H
L1a
(2-(4,4-dimethyl-4,5-dihydro-1,3-oxazol-2-yl)-phenol) is unsubstituted on the phenol ring; ligand H
L1b
(2-(4,4-dimethyl-4,5-dihydro-1,3-oxazol-2-yl)-4-nitrophenol) contains a nitro group in
para
-position to the hydroxy group. In the reaction of precursor complex [ReOCl
3
(PPh
3
)
2
] and H
L1a
the two stereoisomers
cis
/
trans
-
2a
, with respect to chlorido ligands, are formed. The solid state structures of both isomers
cis
- and
trans
-
2a
were determined by single crystal X-ray diffraction analysis. In contrast, with ligand H
L1b
, only the
cis
-isomer
cis
-
2b
was obtained. Ethoxido-complex
4b
is exclusively obtained when precursor [ReOCl
3
(OPPh
3
)(SMe
2
)] is reacted with 2 equiv. of H
L1b
in ethanol in the presence of the base 2,6-dimethylpyridine (lutidine). If no lutidine is added, chlorido-complex [ReOCl(
L1b
)
2
] (
3b
) is obtained. Complexes [ReOCl
2
(PPh
3
)(
L1a
)] (
cis
/
trans
-
2a
), [ReOCl
2
(PPh
3
)(
L1b
)] (
cis
-
2b
), [ReO(OMe)(
L1a
)
2
] (
4a
) and [ReO(OEt)(
L1b
)
2
] (
4b
) were tested as homogeneous catalysts in the benchmark reaction of cyclooctene epoxidation. The influence of isomerism and effects of ligand substitutions on catalytic activity was investigated. Based on the time-conversion plots it can be concluded that
cis
/
trans
-isomerism does not influence catalytic activity, but electron-withdrawing substituents, as in
cis
-
2b
,
3b
and
4b
, show a beneficial effect.
Pairs of stereoisomers and chlorido/alkoxido oxidorhenium(
v
) complexes are described and allow for a systematic investigation of the influence on catalytic activity in standard cyclooctene epoxidation.</description><subject>Catalytic activity</subject><subject>Catalytic converters</subject><subject>Crystallography</subject><subject>Epoxidation</subject><subject>Ethanol</subject><subject>Isomers</subject><subject>Ligands</subject><subject>Nitrophenol</subject><subject>NMR</subject><subject>Nuclear magnetic resonance</subject><subject>Phenols</subject><subject>Precursors</subject><subject>Single crystals</subject><subject>Stereoisomerism</subject><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><recordid>eNp90UtLxDAQAOAiCj4v3oWIl1Wo5tW09Sbra0HwoueSnU4x2jY1SWX335t1RcGDp2Qm3wzDJEkOGT1nVJQXNa0D5SLjsJHsMJnnacmF3Py5c7Wd7Hr_SinnNOM7yTDztkPniekJvLTWmdoS3ddEt292EYPUj3MfTBgD1uQr416wN2M3OSVgu6HFBfpLgk2DEDyxsY0Oul0GAwSHVYEOJmY1BPNhwnI_2Wp06_Hg-9xLnm9vnqb36cPj3Wx69ZCCyFVIQQJDVLLMJGIpJAAWtGkKIXgGmKt5TutMFfG1UVhwDiwrcM5yyKUSimZiL5ms-w7Ovo_oQ9UZD9i2ukc7-opLQWkpmFKRnvyhr3Z0fZxupWROJZNFVGdrBc5677CpBmc67ZYVo9Vq-dU1vX76Wv404uM1dh5-3O_nVEPdRHP0nxGfQ_CNoA</recordid><startdate>20200818</startdate><enddate>20200818</enddate><creator>Schachner, Jörg A</creator><creator>Belaj, Ferdinand</creator><creator>Mösch-Zanetti, Nadia C</creator><general>Royal Society of Chemistry</general><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/0000-0001-9749-2109</orcidid><orcidid>https://orcid.org/0000-0002-1349-6725</orcidid><orcidid>https://orcid.org/0000-0002-1863-4680</orcidid></search><sort><creationdate>20200818</creationdate><title>Isomers in chlorido and alkoxido-substituted oxidorhenium() complexes: effects on catalytic epoxidation activity</title><author>Schachner, Jörg A ; Belaj, Ferdinand ; Mösch-Zanetti, Nadia C</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c376t-c4c1ee64954ee934cce80ff83325ce76b70d56854ef6e822c158eb17c74636053</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>Catalytic activity</topic><topic>Catalytic converters</topic><topic>Crystallography</topic><topic>Epoxidation</topic><topic>Ethanol</topic><topic>Isomers</topic><topic>Ligands</topic><topic>Nitrophenol</topic><topic>NMR</topic><topic>Nuclear magnetic resonance</topic><topic>Phenols</topic><topic>Precursors</topic><topic>Single crystals</topic><topic>Stereoisomerism</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Schachner, Jörg A</creatorcontrib><creatorcontrib>Belaj, Ferdinand</creatorcontrib><creatorcontrib>Mösch-Zanetti, Nadia C</creatorcontrib><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>Schachner, Jörg A</au><au>Belaj, Ferdinand</au><au>Mösch-Zanetti, Nadia C</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Isomers in chlorido and alkoxido-substituted oxidorhenium() complexes: effects on catalytic epoxidation activity</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><date>2020-08-18</date><risdate>2020</risdate><volume>49</volume><issue>32</issue><spage>11142</spage><epage>11149</epage><pages>11142-11149</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract>The syntheses and characterizations of oxidorhenium(
v
) complexes
trans
-dichlorido [ReOCl
2
(PPh
3
)(
L1a
)] (
trans
-
2a
),
cis
-dichlorido [ReOCl
2
(PPh
3
)(
L1b
)] (
cis
-
2b
) and ethoxido-complex [ReO(OEt)(
L1b
)
2
] (
4b
), ligated with the dimethyloxazoline-phenol ligands H
L1a
and H
L1b
are described. The bidentate ligand H
L1a
(2-(4,4-dimethyl-4,5-dihydro-1,3-oxazol-2-yl)-phenol) is unsubstituted on the phenol ring; ligand H
L1b
(2-(4,4-dimethyl-4,5-dihydro-1,3-oxazol-2-yl)-4-nitrophenol) contains a nitro group in
para
-position to the hydroxy group. In the reaction of precursor complex [ReOCl
3
(PPh
3
)
2
] and H
L1a
the two stereoisomers
cis
/
trans
-
2a
, with respect to chlorido ligands, are formed. The solid state structures of both isomers
cis
- and
trans
-
2a
were determined by single crystal X-ray diffraction analysis. In contrast, with ligand H
L1b
, only the
cis
-isomer
cis
-
2b
was obtained. Ethoxido-complex
4b
is exclusively obtained when precursor [ReOCl
3
(OPPh
3
)(SMe
2
)] is reacted with 2 equiv. of H
L1b
in ethanol in the presence of the base 2,6-dimethylpyridine (lutidine). If no lutidine is added, chlorido-complex [ReOCl(
L1b
)
2
] (
3b
) is obtained. Complexes [ReOCl
2
(PPh
3
)(
L1a
)] (
cis
/
trans
-
2a
), [ReOCl
2
(PPh
3
)(
L1b
)] (
cis
-
2b
), [ReO(OMe)(
L1a
)
2
] (
4a
) and [ReO(OEt)(
L1b
)
2
] (
4b
) were tested as homogeneous catalysts in the benchmark reaction of cyclooctene epoxidation. The influence of isomerism and effects of ligand substitutions on catalytic activity was investigated. Based on the time-conversion plots it can be concluded that
cis
/
trans
-isomerism does not influence catalytic activity, but electron-withdrawing substituents, as in
cis
-
2b
,
3b
and
4b
, show a beneficial effect.
Pairs of stereoisomers and chlorido/alkoxido oxidorhenium(
v
) complexes are described and allow for a systematic investigation of the influence on catalytic activity in standard cyclooctene epoxidation.</abstract><cop>Cambridge</cop><pub>Royal Society of Chemistry</pub><doi>10.1039/d0dt02352c</doi><tpages>8</tpages><orcidid>https://orcid.org/0000-0001-9749-2109</orcidid><orcidid>https://orcid.org/0000-0002-1349-6725</orcidid><orcidid>https://orcid.org/0000-0002-1863-4680</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1477-9226 |
| ispartof | Dalton transactions : an international journal of inorganic chemistry, 2020-08, Vol.49 (32), p.11142-11149 |
| issn | 1477-9226 1477-9234 |
| language | eng |
| recordid | cdi_proquest_journals_2434704148 |
| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Catalytic activity Catalytic converters Crystallography Epoxidation Ethanol Isomers Ligands Nitrophenol NMR Nuclear magnetic resonance Phenols Precursors Single crystals Stereoisomerism |
| title | Isomers in chlorido and alkoxido-substituted oxidorhenium() complexes: effects on catalytic epoxidation activity |
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