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Stepwise Functionalization of N 2 at Mo: Nitrido to Imido to Amido – Factors Favoring Amine Elimination from the Amido Complex
Functionalization of nitrido complex [(P Ph P 2 Cy )Mo(N)( I )] by a bis‐silane in concentrated medium generates the hydrido‐imido complex [(P Ph P 2 Cy )Mo(H)(=NSiMe 2 CH 2 CH 2 SiMe 2 H)(I)]. Abstraction of the iodide by thallium salt TlX (X = PF 6 , OTf) results in a second N–Si bond formation an...
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| Published in: | European journal of inorganic chemistry 2020-04, Vol.2020 (15-16), p.1499-1505 |
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| Main Authors: | , , , , , , , |
| Format: | Article |
| Language: | English |
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| cited_by | cdi_FETCH-LOGICAL-c203t-bcc2c2f9880872bdb35cbbdc2e07fb1bc9a982bc2e611d763ae268bb93e5fede3 |
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| cites | cdi_FETCH-LOGICAL-c203t-bcc2c2f9880872bdb35cbbdc2e07fb1bc9a982bc2e611d763ae268bb93e5fede3 |
| container_end_page | 1505 |
| container_issue | 15-16 |
| container_start_page | 1499 |
| container_title | European journal of inorganic chemistry |
| container_volume | 2020 |
| creator | Bennaamane, Soukaina Espada, Maria F. Yagoub, Ikram Saffon‐Merceron, Nathalie Nebra, Noel Fustier‐Boutignon, Marie Clot, Eric Mézailles, Nicolas |
| description | Functionalization of nitrido complex [(P
Ph
P
2
Cy
)Mo(N)(
I
)] by a bis‐silane in concentrated medium generates the hydrido‐imido complex [(P
Ph
P
2
Cy
)Mo(H)(=NSiMe
2
CH
2
CH
2
SiMe
2
H)(I)]. Abstraction of the iodide by thallium salt TlX (X = PF
6
, OTf) results in a second N–Si bond formation and forms the bis‐hydride amide complex [(P
Ph
P
2
Cy
)Mo(H)
2
(NSiMe
2
CH
2
CH
2
SiMe
2
)]
+
. An alternative synthesis relies on the abstraction of the iodide from the nitride complex [(P
Ph
P
2
Cy
)Mo(N)(I)] to generate the corresponding cationic complex [(P
Ph
P
2
Cy
)Mo(N)]
+
followed by addition of the bis‐silane. Addition of PMe
3
to the [(P
Ph
P
2
Cy
)Mo(H)
2
(NSiMe
2
CH
2
CH
2
SiMe
2
)]
+
complex liberates the silylamine and forms the Mo
(II)
cationic complex [(P
Ph
P
2
Cy
)Mo(H)(PMe
3
)]
+
. DFT calculations rationalizing the observed reactivity are presented. |
| doi_str_mv | 10.1002/ejic.201901295 |
| format | article |
| fullrecord | <record><control><sourceid>hal_cross</sourceid><recordid>TN_cdi_hal_primary_oai_HAL_hal_03012876v1</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>oai_HAL_hal_03012876v1</sourcerecordid><originalsourceid>FETCH-LOGICAL-c203t-bcc2c2f9880872bdb35cbbdc2e07fb1bc9a982bc2e611d763ae268bb93e5fede3</originalsourceid><addsrcrecordid>eNo9kL1OwzAUhS0EEqWwMntlSLm228Rmq6qWViplAObIdhzqKokr25Sfqe_AG_IkJLRiOt-999wzHISuCQwIAL01G6sHFIgAQsXoBPUICJFAyulpy0M2TIgY8nN0EcIGABiwtIf2T9Fs320wePbW6GhdIyv7JTvArsQrTLGM-MHd4ZWN3hYOR4cX9RHGf_Cz_8YzqaPzodWd87Z57U6NwdPKtnqIK72rcVyb49fE1dvKfFyis1JWwVwdtY9eZtPnyTxZPt4vJuNloimwmCitqaal4Bx4RlWh2EgrVWhqICsVUVpIwalq55SQIkuZNDTlSglmRqUpDOujm0PuWlb51tta-s_cSZvPx8u827WFEMqzdEda7-Dg1d6F4E35_0Ag77rOu67z_67ZLzsSdFs</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Stepwise Functionalization of N 2 at Mo: Nitrido to Imido to Amido – Factors Favoring Amine Elimination from the Amido Complex</title><source>Wiley</source><creator>Bennaamane, Soukaina ; Espada, Maria F. ; Yagoub, Ikram ; Saffon‐Merceron, Nathalie ; Nebra, Noel ; Fustier‐Boutignon, Marie ; Clot, Eric ; Mézailles, Nicolas</creator><creatorcontrib>Bennaamane, Soukaina ; Espada, Maria F. ; Yagoub, Ikram ; Saffon‐Merceron, Nathalie ; Nebra, Noel ; Fustier‐Boutignon, Marie ; Clot, Eric ; Mézailles, Nicolas</creatorcontrib><description>Functionalization of nitrido complex [(P
Ph
P
2
Cy
)Mo(N)(
I
)] by a bis‐silane in concentrated medium generates the hydrido‐imido complex [(P
Ph
P
2
Cy
)Mo(H)(=NSiMe
2
CH
2
CH
2
SiMe
2
H)(I)]. Abstraction of the iodide by thallium salt TlX (X = PF
6
, OTf) results in a second N–Si bond formation and forms the bis‐hydride amide complex [(P
Ph
P
2
Cy
)Mo(H)
2
(NSiMe
2
CH
2
CH
2
SiMe
2
)]
+
. An alternative synthesis relies on the abstraction of the iodide from the nitride complex [(P
Ph
P
2
Cy
)Mo(N)(I)] to generate the corresponding cationic complex [(P
Ph
P
2
Cy
)Mo(N)]
+
followed by addition of the bis‐silane. Addition of PMe
3
to the [(P
Ph
P
2
Cy
)Mo(H)
2
(NSiMe
2
CH
2
CH
2
SiMe
2
)]
+
complex liberates the silylamine and forms the Mo
(II)
cationic complex [(P
Ph
P
2
Cy
)Mo(H)(PMe
3
)]
+
. DFT calculations rationalizing the observed reactivity are presented.</description><identifier>ISSN: 1434-1948</identifier><identifier>EISSN: 1099-0682</identifier><identifier>DOI: 10.1002/ejic.201901295</identifier><language>eng</language><publisher>Wiley-VCH Verlag</publisher><subject>Catalysis ; Chemical Sciences ; Coordination chemistry ; or physical chemistry ; Theoretical and</subject><ispartof>European journal of inorganic chemistry, 2020-04, Vol.2020 (15-16), p.1499-1505</ispartof><rights>Distributed under a Creative Commons Attribution 4.0 International License</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c203t-bcc2c2f9880872bdb35cbbdc2e07fb1bc9a982bc2e611d763ae268bb93e5fede3</citedby><cites>FETCH-LOGICAL-c203t-bcc2c2f9880872bdb35cbbdc2e07fb1bc9a982bc2e611d763ae268bb93e5fede3</cites><orcidid>0000-0001-8735-6285 ; 0000-0002-0301-4163 ; 0000-0002-4209-9235 ; 0000-0001-8332-5545 ; 0000-0002-1180-3680</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,314,780,784,885,27924,27925</link.rule.ids><backlink>$$Uhttps://hal.science/hal-03012876$$DView record in HAL$$Hfree_for_read</backlink></links><search><creatorcontrib>Bennaamane, Soukaina</creatorcontrib><creatorcontrib>Espada, Maria F.</creatorcontrib><creatorcontrib>Yagoub, Ikram</creatorcontrib><creatorcontrib>Saffon‐Merceron, Nathalie</creatorcontrib><creatorcontrib>Nebra, Noel</creatorcontrib><creatorcontrib>Fustier‐Boutignon, Marie</creatorcontrib><creatorcontrib>Clot, Eric</creatorcontrib><creatorcontrib>Mézailles, Nicolas</creatorcontrib><title>Stepwise Functionalization of N 2 at Mo: Nitrido to Imido to Amido – Factors Favoring Amine Elimination from the Amido Complex</title><title>European journal of inorganic chemistry</title><description>Functionalization of nitrido complex [(P
Ph
P
2
Cy
)Mo(N)(
I
)] by a bis‐silane in concentrated medium generates the hydrido‐imido complex [(P
Ph
P
2
Cy
)Mo(H)(=NSiMe
2
CH
2
CH
2
SiMe
2
H)(I)]. Abstraction of the iodide by thallium salt TlX (X = PF
6
, OTf) results in a second N–Si bond formation and forms the bis‐hydride amide complex [(P
Ph
P
2
Cy
)Mo(H)
2
(NSiMe
2
CH
2
CH
2
SiMe
2
)]
+
. An alternative synthesis relies on the abstraction of the iodide from the nitride complex [(P
Ph
P
2
Cy
)Mo(N)(I)] to generate the corresponding cationic complex [(P
Ph
P
2
Cy
)Mo(N)]
+
followed by addition of the bis‐silane. Addition of PMe
3
to the [(P
Ph
P
2
Cy
)Mo(H)
2
(NSiMe
2
CH
2
CH
2
SiMe
2
)]
+
complex liberates the silylamine and forms the Mo
(II)
cationic complex [(P
Ph
P
2
Cy
)Mo(H)(PMe
3
)]
+
. DFT calculations rationalizing the observed reactivity are presented.</description><subject>Catalysis</subject><subject>Chemical Sciences</subject><subject>Coordination chemistry</subject><subject>or physical chemistry</subject><subject>Theoretical and</subject><issn>1434-1948</issn><issn>1099-0682</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><recordid>eNo9kL1OwzAUhS0EEqWwMntlSLm228Rmq6qWViplAObIdhzqKokr25Sfqe_AG_IkJLRiOt-999wzHISuCQwIAL01G6sHFIgAQsXoBPUICJFAyulpy0M2TIgY8nN0EcIGABiwtIf2T9Fs320wePbW6GhdIyv7JTvArsQrTLGM-MHd4ZWN3hYOR4cX9RHGf_Cz_8YzqaPzodWd87Z57U6NwdPKtnqIK72rcVyb49fE1dvKfFyis1JWwVwdtY9eZtPnyTxZPt4vJuNloimwmCitqaal4Bx4RlWh2EgrVWhqICsVUVpIwalq55SQIkuZNDTlSglmRqUpDOujm0PuWlb51tta-s_cSZvPx8u827WFEMqzdEda7-Dg1d6F4E35_0Ag77rOu67z_67ZLzsSdFs</recordid><startdate>20200430</startdate><enddate>20200430</enddate><creator>Bennaamane, Soukaina</creator><creator>Espada, Maria F.</creator><creator>Yagoub, Ikram</creator><creator>Saffon‐Merceron, Nathalie</creator><creator>Nebra, Noel</creator><creator>Fustier‐Boutignon, Marie</creator><creator>Clot, Eric</creator><creator>Mézailles, Nicolas</creator><general>Wiley-VCH Verlag</general><scope>AAYXX</scope><scope>CITATION</scope><scope>1XC</scope><scope>VOOES</scope><orcidid>https://orcid.org/0000-0001-8735-6285</orcidid><orcidid>https://orcid.org/0000-0002-0301-4163</orcidid><orcidid>https://orcid.org/0000-0002-4209-9235</orcidid><orcidid>https://orcid.org/0000-0001-8332-5545</orcidid><orcidid>https://orcid.org/0000-0002-1180-3680</orcidid></search><sort><creationdate>20200430</creationdate><title>Stepwise Functionalization of N 2 at Mo: Nitrido to Imido to Amido – Factors Favoring Amine Elimination from the Amido Complex</title><author>Bennaamane, Soukaina ; Espada, Maria F. ; Yagoub, Ikram ; Saffon‐Merceron, Nathalie ; Nebra, Noel ; Fustier‐Boutignon, Marie ; Clot, Eric ; Mézailles, Nicolas</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c203t-bcc2c2f9880872bdb35cbbdc2e07fb1bc9a982bc2e611d763ae268bb93e5fede3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>Catalysis</topic><topic>Chemical Sciences</topic><topic>Coordination chemistry</topic><topic>or physical chemistry</topic><topic>Theoretical and</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Bennaamane, Soukaina</creatorcontrib><creatorcontrib>Espada, Maria F.</creatorcontrib><creatorcontrib>Yagoub, Ikram</creatorcontrib><creatorcontrib>Saffon‐Merceron, Nathalie</creatorcontrib><creatorcontrib>Nebra, Noel</creatorcontrib><creatorcontrib>Fustier‐Boutignon, Marie</creatorcontrib><creatorcontrib>Clot, Eric</creatorcontrib><creatorcontrib>Mézailles, Nicolas</creatorcontrib><collection>CrossRef</collection><collection>Hyper Article en Ligne (HAL)</collection><collection>Hyper Article en Ligne (HAL) (Open Access)</collection><jtitle>European journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Bennaamane, Soukaina</au><au>Espada, Maria F.</au><au>Yagoub, Ikram</au><au>Saffon‐Merceron, Nathalie</au><au>Nebra, Noel</au><au>Fustier‐Boutignon, Marie</au><au>Clot, Eric</au><au>Mézailles, Nicolas</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Stepwise Functionalization of N 2 at Mo: Nitrido to Imido to Amido – Factors Favoring Amine Elimination from the Amido Complex</atitle><jtitle>European journal of inorganic chemistry</jtitle><date>2020-04-30</date><risdate>2020</risdate><volume>2020</volume><issue>15-16</issue><spage>1499</spage><epage>1505</epage><pages>1499-1505</pages><issn>1434-1948</issn><eissn>1099-0682</eissn><abstract>Functionalization of nitrido complex [(P
Ph
P
2
Cy
)Mo(N)(
I
)] by a bis‐silane in concentrated medium generates the hydrido‐imido complex [(P
Ph
P
2
Cy
)Mo(H)(=NSiMe
2
CH
2
CH
2
SiMe
2
H)(I)]. Abstraction of the iodide by thallium salt TlX (X = PF
6
, OTf) results in a second N–Si bond formation and forms the bis‐hydride amide complex [(P
Ph
P
2
Cy
)Mo(H)
2
(NSiMe
2
CH
2
CH
2
SiMe
2
)]
+
. An alternative synthesis relies on the abstraction of the iodide from the nitride complex [(P
Ph
P
2
Cy
)Mo(N)(I)] to generate the corresponding cationic complex [(P
Ph
P
2
Cy
)Mo(N)]
+
followed by addition of the bis‐silane. Addition of PMe
3
to the [(P
Ph
P
2
Cy
)Mo(H)
2
(NSiMe
2
CH
2
CH
2
SiMe
2
)]
+
complex liberates the silylamine and forms the Mo
(II)
cationic complex [(P
Ph
P
2
Cy
)Mo(H)(PMe
3
)]
+
. DFT calculations rationalizing the observed reactivity are presented.</abstract><pub>Wiley-VCH Verlag</pub><doi>10.1002/ejic.201901295</doi><tpages>7</tpages><orcidid>https://orcid.org/0000-0001-8735-6285</orcidid><orcidid>https://orcid.org/0000-0002-0301-4163</orcidid><orcidid>https://orcid.org/0000-0002-4209-9235</orcidid><orcidid>https://orcid.org/0000-0001-8332-5545</orcidid><orcidid>https://orcid.org/0000-0002-1180-3680</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1434-1948 |
| ispartof | European journal of inorganic chemistry, 2020-04, Vol.2020 (15-16), p.1499-1505 |
| issn | 1434-1948 1099-0682 |
| language | eng |
| recordid | cdi_hal_primary_oai_HAL_hal_03012876v1 |
| source | Wiley |
| subjects | Catalysis Chemical Sciences Coordination chemistry or physical chemistry Theoretical and |
| title | Stepwise Functionalization of N 2 at Mo: Nitrido to Imido to Amido – Factors Favoring Amine Elimination from the Amido Complex |
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