14-Electron Rh and Ir silylphosphine complexes and their catalytic activity in alkene functionalization with hydrosilanes
Herein we report an experimental and computational study of a family of four coordinated 14-electron complexes of Rh( iii ) devoid of agostic interactions. The complexes [X-Rh(κ 3 ( P,Si,Si )PhP( o -C 6 H 4 CH 2 Si i Pr 2 ) 2 ], where X = Cl ( Rh-1 ), Br ( Rh-2 ), I ( Rh-3 ), OTf ( Rh-4 ), Cl·GaCl 3...
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| Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2021-09, Vol.5 (34), p.11783-11792 |
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| container_title | Dalton transactions : an international journal of inorganic chemistry |
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| creator | Abeynayake, Niroshani S Zamora-Moreno, Julio Gorla, Saidulu Donnadieu, Bruno Muñoz-Hernández, Miguel A Montiel-Palma, Virginia |
| description | Herein we report an experimental and computational study of a family of four coordinated 14-electron complexes of Rh(
iii
) devoid of agostic interactions. The complexes [X-Rh(κ
3
(
P,Si,Si
)PhP(
o
-C
6
H
4
CH
2
Si
i
Pr
2
)
2
], where X = Cl (
Rh-1
), Br (
Rh-2
), I (
Rh-3
), OTf (
Rh-4
), Cl·GaCl
3
(
Rh-5
); derive from a bis(silyl)-
o
-tolylphosphine with isopropyl substituents on the Si atoms. All five complexes display a sawhorse geometry around Rh and exhibit similar spectroscopic and structural properties. The catalytic activity of these complexes and [Cl-Ir(κ
3
(
P,Si,Si
)PhP(
o
-C
6
H
4
CH
2
Si
i
Pr
2
)
2
],
Ir-1
, in styrene and aliphatic alkene functionalizations with hydrosilanes is disclosed. We show that
Rh-1
catalyzes effectively the dehydrogenative silylation of styrene with Et
3
SiH in toluene while it leads to hydrosilylation products in acetonitrile.
Rh-1
is an excellent catalyst in the sequential isomerization/hydrosilylation of terminal and remote aliphatic alkenes with Et
3
SiH including hexene isomers, leading efficiently and selectively to the terminal anti-Markonikov hydrosilylation product in all cases. With aliphatic alkenes, no hydrogenation products are observed. Conversely, catalysis of the same hexene isomers by
Ir-1
renders allyl silanes, the tandem isomerization/dehydrogenative silylation products. A mechanistic proposal is made to explain the catalysis with these M(
iii
) complexes.
14-electron Rh and Ir species as robust catalysts for silicon functionalization. |
| doi_str_mv | 10.1039/d1dt00677k |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_2559661660</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2559661660</sourcerecordid><originalsourceid>FETCH-LOGICAL-c314t-ec492a724f42100dc58107c6996b115f8223c3fb43360d5690862b1ce6331f913</originalsourceid><addsrcrecordid>eNpdkd9LwzAQx4soOKcvvgsBX0So5pI2XR5lmz9wIMh8Llma0mxZU5NUrX-93SYTfLovd5877ss3is4B3wCm_LaAImDMsmx1EA0gybKYE5oc7jVhx9GJ90uMCcEpGUQdJPHUKBmcrdFrhURdoCeHvDadaSrrm0rXCkm7boz6Un47D5XSDkkRhOmClkjIoD906JCukTAr1S-Ubd03bS2M_hYbgT51qFDVFc72t0Wt_Gl0VArj1dlvHUZv99P5-DGevTw8je9msaSQhFjJhBORkaRMCGBcyHQEOJOMc7YASMsRIVTScpFQynCRMo5HjCxAKkYplBzoMLra3W2cfW-VD_lae6nM5gnb-pykKWcMGMM9evkPXdrW9SY2FGMEZ5CRnrreUbL34p0q88bptXBdDjjfpJBPYDLfpvDcwxc72Hm55_5Soj_oWIRB</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2566207172</pqid></control><display><type>article</type><title>14-Electron Rh and Ir silylphosphine complexes and their catalytic activity in alkene functionalization with hydrosilanes</title><source>Royal Society Of Chemistry Journals 2008-</source><source>Alma/SFX Local Collection</source><creator>Abeynayake, Niroshani S ; Zamora-Moreno, Julio ; Gorla, Saidulu ; Donnadieu, Bruno ; Muñoz-Hernández, Miguel A ; Montiel-Palma, Virginia</creator><creatorcontrib>Abeynayake, Niroshani S ; Zamora-Moreno, Julio ; Gorla, Saidulu ; Donnadieu, Bruno ; Muñoz-Hernández, Miguel A ; Montiel-Palma, Virginia</creatorcontrib><description>Herein we report an experimental and computational study of a family of four coordinated 14-electron complexes of Rh(
iii
) devoid of agostic interactions. The complexes [X-Rh(κ
3
(
P,Si,Si
)PhP(
o
-C
6
H
4
CH
2
Si
i
Pr
2
)
2
], where X = Cl (
Rh-1
), Br (
Rh-2
), I (
Rh-3
), OTf (
Rh-4
), Cl·GaCl
3
(
Rh-5
); derive from a bis(silyl)-
o
-tolylphosphine with isopropyl substituents on the Si atoms. All five complexes display a sawhorse geometry around Rh and exhibit similar spectroscopic and structural properties. The catalytic activity of these complexes and [Cl-Ir(κ
3
(
P,Si,Si
)PhP(
o
-C
6
H
4
CH
2
Si
i
Pr
2
)
2
],
Ir-1
, in styrene and aliphatic alkene functionalizations with hydrosilanes is disclosed. We show that
Rh-1
catalyzes effectively the dehydrogenative silylation of styrene with Et
3
SiH in toluene while it leads to hydrosilylation products in acetonitrile.
Rh-1
is an excellent catalyst in the sequential isomerization/hydrosilylation of terminal and remote aliphatic alkenes with Et
3
SiH including hexene isomers, leading efficiently and selectively to the terminal anti-Markonikov hydrosilylation product in all cases. With aliphatic alkenes, no hydrogenation products are observed. Conversely, catalysis of the same hexene isomers by
Ir-1
renders allyl silanes, the tandem isomerization/dehydrogenative silylation products. A mechanistic proposal is made to explain the catalysis with these M(
iii
) complexes.
14-electron Rh and Ir species as robust catalysts for silicon functionalization.</description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/d1dt00677k</identifier><language>eng</language><publisher>Cambridge: Royal Society of Chemistry</publisher><subject>Acetonitrile ; Aliphatic compounds ; Alkenes ; Cartesian coordinates ; Catalysis ; Catalytic activity ; Crystallography ; Dehydrogenation ; Format ; Frames ; Gallium chloride ; Hydrosilylation ; Isomerization ; Isomers ; NMR ; Nuclear magnetic resonance ; Rhodium ; Sawing ; Styrenes ; Toluene</subject><ispartof>Dalton transactions : an international journal of inorganic chemistry, 2021-09, Vol.5 (34), p.11783-11792</ispartof><rights>Copyright Royal Society of Chemistry 2021</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c314t-ec492a724f42100dc58107c6996b115f8223c3fb43360d5690862b1ce6331f913</citedby><cites>FETCH-LOGICAL-c314t-ec492a724f42100dc58107c6996b115f8223c3fb43360d5690862b1ce6331f913</cites><orcidid>0000-0003-0134-9020</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>Abeynayake, Niroshani S</creatorcontrib><creatorcontrib>Zamora-Moreno, Julio</creatorcontrib><creatorcontrib>Gorla, Saidulu</creatorcontrib><creatorcontrib>Donnadieu, Bruno</creatorcontrib><creatorcontrib>Muñoz-Hernández, Miguel A</creatorcontrib><creatorcontrib>Montiel-Palma, Virginia</creatorcontrib><title>14-Electron Rh and Ir silylphosphine complexes and their catalytic activity in alkene functionalization with hydrosilanes</title><title>Dalton transactions : an international journal of inorganic chemistry</title><description>Herein we report an experimental and computational study of a family of four coordinated 14-electron complexes of Rh(
iii
) devoid of agostic interactions. The complexes [X-Rh(κ
3
(
P,Si,Si
)PhP(
o
-C
6
H
4
CH
2
Si
i
Pr
2
)
2
], where X = Cl (
Rh-1
), Br (
Rh-2
), I (
Rh-3
), OTf (
Rh-4
), Cl·GaCl
3
(
Rh-5
); derive from a bis(silyl)-
o
-tolylphosphine with isopropyl substituents on the Si atoms. All five complexes display a sawhorse geometry around Rh and exhibit similar spectroscopic and structural properties. The catalytic activity of these complexes and [Cl-Ir(κ
3
(
P,Si,Si
)PhP(
o
-C
6
H
4
CH
2
Si
i
Pr
2
)
2
],
Ir-1
, in styrene and aliphatic alkene functionalizations with hydrosilanes is disclosed. We show that
Rh-1
catalyzes effectively the dehydrogenative silylation of styrene with Et
3
SiH in toluene while it leads to hydrosilylation products in acetonitrile.
Rh-1
is an excellent catalyst in the sequential isomerization/hydrosilylation of terminal and remote aliphatic alkenes with Et
3
SiH including hexene isomers, leading efficiently and selectively to the terminal anti-Markonikov hydrosilylation product in all cases. With aliphatic alkenes, no hydrogenation products are observed. Conversely, catalysis of the same hexene isomers by
Ir-1
renders allyl silanes, the tandem isomerization/dehydrogenative silylation products. A mechanistic proposal is made to explain the catalysis with these M(
iii
) complexes.
14-electron Rh and Ir species as robust catalysts for silicon functionalization.</description><subject>Acetonitrile</subject><subject>Aliphatic compounds</subject><subject>Alkenes</subject><subject>Cartesian coordinates</subject><subject>Catalysis</subject><subject>Catalytic activity</subject><subject>Crystallography</subject><subject>Dehydrogenation</subject><subject>Format</subject><subject>Frames</subject><subject>Gallium chloride</subject><subject>Hydrosilylation</subject><subject>Isomerization</subject><subject>Isomers</subject><subject>NMR</subject><subject>Nuclear magnetic resonance</subject><subject>Rhodium</subject><subject>Sawing</subject><subject>Styrenes</subject><subject>Toluene</subject><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><recordid>eNpdkd9LwzAQx4soOKcvvgsBX0So5pI2XR5lmz9wIMh8Llma0mxZU5NUrX-93SYTfLovd5877ss3is4B3wCm_LaAImDMsmx1EA0gybKYE5oc7jVhx9GJ90uMCcEpGUQdJPHUKBmcrdFrhURdoCeHvDadaSrrm0rXCkm7boz6Un47D5XSDkkRhOmClkjIoD906JCukTAr1S-Ubd03bS2M_hYbgT51qFDVFc72t0Wt_Gl0VArj1dlvHUZv99P5-DGevTw8je9msaSQhFjJhBORkaRMCGBcyHQEOJOMc7YASMsRIVTScpFQynCRMo5HjCxAKkYplBzoMLra3W2cfW-VD_lae6nM5gnb-pykKWcMGMM9evkPXdrW9SY2FGMEZ5CRnrreUbL34p0q88bptXBdDjjfpJBPYDLfpvDcwxc72Hm55_5Soj_oWIRB</recordid><startdate>20210914</startdate><enddate>20210914</enddate><creator>Abeynayake, Niroshani S</creator><creator>Zamora-Moreno, Julio</creator><creator>Gorla, Saidulu</creator><creator>Donnadieu, Bruno</creator><creator>Muñoz-Hernández, Miguel A</creator><creator>Montiel-Palma, Virginia</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/0000-0003-0134-9020</orcidid></search><sort><creationdate>20210914</creationdate><title>14-Electron Rh and Ir silylphosphine complexes and their catalytic activity in alkene functionalization with hydrosilanes</title><author>Abeynayake, Niroshani S ; Zamora-Moreno, Julio ; Gorla, Saidulu ; Donnadieu, Bruno ; Muñoz-Hernández, Miguel A ; Montiel-Palma, Virginia</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c314t-ec492a724f42100dc58107c6996b115f8223c3fb43360d5690862b1ce6331f913</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>Acetonitrile</topic><topic>Aliphatic compounds</topic><topic>Alkenes</topic><topic>Cartesian coordinates</topic><topic>Catalysis</topic><topic>Catalytic activity</topic><topic>Crystallography</topic><topic>Dehydrogenation</topic><topic>Format</topic><topic>Frames</topic><topic>Gallium chloride</topic><topic>Hydrosilylation</topic><topic>Isomerization</topic><topic>Isomers</topic><topic>NMR</topic><topic>Nuclear magnetic resonance</topic><topic>Rhodium</topic><topic>Sawing</topic><topic>Styrenes</topic><topic>Toluene</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Abeynayake, Niroshani S</creatorcontrib><creatorcontrib>Zamora-Moreno, Julio</creatorcontrib><creatorcontrib>Gorla, Saidulu</creatorcontrib><creatorcontrib>Donnadieu, Bruno</creatorcontrib><creatorcontrib>Muñoz-Hernández, Miguel A</creatorcontrib><creatorcontrib>Montiel-Palma, Virginia</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>Abeynayake, Niroshani S</au><au>Zamora-Moreno, Julio</au><au>Gorla, Saidulu</au><au>Donnadieu, Bruno</au><au>Muñoz-Hernández, Miguel A</au><au>Montiel-Palma, Virginia</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>14-Electron Rh and Ir silylphosphine complexes and their catalytic activity in alkene functionalization with hydrosilanes</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><date>2021-09-14</date><risdate>2021</risdate><volume>5</volume><issue>34</issue><spage>11783</spage><epage>11792</epage><pages>11783-11792</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract>Herein we report an experimental and computational study of a family of four coordinated 14-electron complexes of Rh(
iii
) devoid of agostic interactions. The complexes [X-Rh(κ
3
(
P,Si,Si
)PhP(
o
-C
6
H
4
CH
2
Si
i
Pr
2
)
2
], where X = Cl (
Rh-1
), Br (
Rh-2
), I (
Rh-3
), OTf (
Rh-4
), Cl·GaCl
3
(
Rh-5
); derive from a bis(silyl)-
o
-tolylphosphine with isopropyl substituents on the Si atoms. All five complexes display a sawhorse geometry around Rh and exhibit similar spectroscopic and structural properties. The catalytic activity of these complexes and [Cl-Ir(κ
3
(
P,Si,Si
)PhP(
o
-C
6
H
4
CH
2
Si
i
Pr
2
)
2
],
Ir-1
, in styrene and aliphatic alkene functionalizations with hydrosilanes is disclosed. We show that
Rh-1
catalyzes effectively the dehydrogenative silylation of styrene with Et
3
SiH in toluene while it leads to hydrosilylation products in acetonitrile.
Rh-1
is an excellent catalyst in the sequential isomerization/hydrosilylation of terminal and remote aliphatic alkenes with Et
3
SiH including hexene isomers, leading efficiently and selectively to the terminal anti-Markonikov hydrosilylation product in all cases. With aliphatic alkenes, no hydrogenation products are observed. Conversely, catalysis of the same hexene isomers by
Ir-1
renders allyl silanes, the tandem isomerization/dehydrogenative silylation products. A mechanistic proposal is made to explain the catalysis with these M(
iii
) complexes.
14-electron Rh and Ir species as robust catalysts for silicon functionalization.</abstract><cop>Cambridge</cop><pub>Royal Society of Chemistry</pub><doi>10.1039/d1dt00677k</doi><tpages>1</tpages><orcidid>https://orcid.org/0000-0003-0134-9020</orcidid></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1477-9226 |
| ispartof | Dalton transactions : an international journal of inorganic chemistry, 2021-09, Vol.5 (34), p.11783-11792 |
| issn | 1477-9226 1477-9234 |
| language | eng |
| recordid | cdi_proquest_miscellaneous_2559661660 |
| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Acetonitrile Aliphatic compounds Alkenes Cartesian coordinates Catalysis Catalytic activity Crystallography Dehydrogenation Format Frames Gallium chloride Hydrosilylation Isomerization Isomers NMR Nuclear magnetic resonance Rhodium Sawing Styrenes Toluene |
| title | 14-Electron Rh and Ir silylphosphine complexes and their catalytic activity in alkene functionalization with hydrosilanes |
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