Synthesis and reactivity of an N-triphos Mo(0) dinitrogen complex
The preparation and reactivity of a novel molybdenum dinitrogen complex supported by a nitrogen-centred tripodal phosphine ligand (N-triphos, N(CH 2 PPh 2 ) 3 , NP 3 Ph ) are reported. Reaction of N-triphos with [MoX 3 (THF) 3 ] (X = Cl, Br, I) gave the Mo( iii ) complex [MoX 3 (κ 2 -NP 3 Ph )(THF)]...
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Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2018, Vol.47 (33), p.11386-11396 |
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creator | Apps, Samantha L White, Andrew J. P Miller, Philip W Long, Nicholas J |
description | The preparation and reactivity of a novel molybdenum dinitrogen complex supported by a nitrogen-centred tripodal phosphine ligand (N-triphos, N(CH
2
PPh
2
)
3
, NP
3
Ph
) are reported. Reaction of N-triphos with [MoX
3
(THF)
3
] (X = Cl, Br, I) gave the Mo(
iii
) complex [MoX
3
(κ
2
-NP
3
Ph
)(THF)] (
1
), where bidentate N-triphos coordination was observed. Reduction of this complex in the presence of dppm (bis(diphenylphosphino)methane) gave the dinitrogen complex [Mo(N
2
)(dppm)(κ
3
-NP
3
Ph
)] (
2
), which exhibits moderate dinitrogen activation. An additional hydride complex, [Mo(H)
2
(dppm)(κ
3
-NP
3
Ph
)] (
4
), was produced either as a minor side product during the reduction step, or as a major product by direct hydrogenation of the dinitrogen complex
2
. The reactivity of the dinitrogen complex
2
with a range of Lewis acids was also investigated. At low temperatures, protic or borane Lewis acids (H
+
, BBr
3
and tris(pentafluorophenyl)borane (BCF)) were found to coordinate to the apical nitrogen atom of the N-triphos ligand, with no conclusive evidence of any functionalisation of the dinitrogen ligand. Alkali metal Lewis acid addition to
2
resulted in the unexpected rearrangement of the N-triphos ligand to form [Mo(dppm)(PMePh
2
)(PCP)][B(C
6
F
5
)
4
] (
7
), where PCP, [Ph
2
PCNHCH
2
PPh
2
] is the carbenic ligand formed upon rearrangement from the reaction of
2
with M[B(C
6
F
5
)
4
] (M = Li, Na or K). Single crystal X-ray diffraction of complexes
1
,
2
,
4
and
7
provided structural confirmation of the N-triphos molybdenum complexes described.
N-Triphos/Mo(0)-dinitrogen reactivity: hydrogenation; Lewis acid addition; and alkali metal mediated ligand rearrangement. |
doi_str_mv | 10.1039/c8dt02471e |
format | Article |
fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_journals_2090562868</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2080829324</sourcerecordid><originalsourceid>FETCH-LOGICAL-c439t-975e2f8da3a7a6ba55e034dc9513a4d53a38129773f58da843a671cc705298ae3</originalsourceid><addsrcrecordid>eNpd0c9LwzAUB_AgitPpxbtS8DKFan42yXHM-QOmHpznkqWp62ibmaTi_nujmxM85fHeh8fjGwBOELxCkMhrLYoAMeXI7IADRDlPJSZ0d1vjrAcOvV9AiDFkeB_0CIRZJPgADF9WbZgbX_lEtUXijNKh-qjCKrFl7CRPaXDVcm598mgH8CIpqrYKzr6ZNtG2Wdbm8wjslar25njz9sHr7Xg6uk8nz3cPo-Ek1ZTIkErODC5FoYjiKpspxgwktNCSIaJowYgiAmHJOSlZVIISlXGkNY8XS6EM6YPBeu_S2ffO-JA3ldemrlVrbOdzDAUUWBJMIz3_Rxe2c228LioJWYZFJqK6XCvtrPfOlPnSVY1yqxzB_DvYfCRupj_BjiM-26zsZo0ptvQ3yQhO18B5vZ3-_Qz5AqkTeng</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2090562868</pqid></control><display><type>article</type><title>Synthesis and reactivity of an N-triphos Mo(0) dinitrogen complex</title><source>Royal Society Of Chemistry Journals 2008-</source><source>Alma/SFX Local Collection</source><creator>Apps, Samantha L ; White, Andrew J. P ; Miller, Philip W ; Long, Nicholas J</creator><creatorcontrib>Apps, Samantha L ; White, Andrew J. P ; Miller, Philip W ; Long, Nicholas J</creatorcontrib><description>The preparation and reactivity of a novel molybdenum dinitrogen complex supported by a nitrogen-centred tripodal phosphine ligand (N-triphos, N(CH
2
PPh
2
)
3
, NP
3
Ph
) are reported. Reaction of N-triphos with [MoX
3
(THF)
3
] (X = Cl, Br, I) gave the Mo(
iii
) complex [MoX
3
(κ
2
-NP
3
Ph
)(THF)] (
1
), where bidentate N-triphos coordination was observed. Reduction of this complex in the presence of dppm (bis(diphenylphosphino)methane) gave the dinitrogen complex [Mo(N
2
)(dppm)(κ
3
-NP
3
Ph
)] (
2
), which exhibits moderate dinitrogen activation. An additional hydride complex, [Mo(H)
2
(dppm)(κ
3
-NP
3
Ph
)] (
4
), was produced either as a minor side product during the reduction step, or as a major product by direct hydrogenation of the dinitrogen complex
2
. The reactivity of the dinitrogen complex
2
with a range of Lewis acids was also investigated. At low temperatures, protic or borane Lewis acids (H
+
, BBr
3
and tris(pentafluorophenyl)borane (BCF)) were found to coordinate to the apical nitrogen atom of the N-triphos ligand, with no conclusive evidence of any functionalisation of the dinitrogen ligand. Alkali metal Lewis acid addition to
2
resulted in the unexpected rearrangement of the N-triphos ligand to form [Mo(dppm)(PMePh
2
)(PCP)][B(C
6
F
5
)
4
] (
7
), where PCP, [Ph
2
PCNHCH
2
PPh
2
] is the carbenic ligand formed upon rearrangement from the reaction of
2
with M[B(C
6
F
5
)
4
] (M = Li, Na or K). Single crystal X-ray diffraction of complexes
1
,
2
,
4
and
7
provided structural confirmation of the N-triphos molybdenum complexes described.
N-Triphos/Mo(0)-dinitrogen reactivity: hydrogenation; Lewis acid addition; and alkali metal mediated ligand rearrangement.</description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/c8dt02471e</identifier><identifier>PMID: 30062342</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Alkali metals ; Crystal structure ; Lewis acid ; Ligands ; Molybdenum ; Nitrogen compounds ; Reactivity ; Reduction ; Single crystals ; X-ray diffraction</subject><ispartof>Dalton transactions : an international journal of inorganic chemistry, 2018, Vol.47 (33), p.11386-11396</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-975e2f8da3a7a6ba55e034dc9513a4d53a38129773f58da843a671cc705298ae3</citedby><cites>FETCH-LOGICAL-c439t-975e2f8da3a7a6ba55e034dc9513a4d53a38129773f58da843a671cc705298ae3</cites><orcidid>0000-0002-8394-2516 ; 0000-0002-8298-938X ; 0000-0002-9970-5857</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/30062342$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Apps, Samantha L</creatorcontrib><creatorcontrib>White, Andrew J. P</creatorcontrib><creatorcontrib>Miller, Philip W</creatorcontrib><creatorcontrib>Long, Nicholas J</creatorcontrib><title>Synthesis and reactivity of an N-triphos Mo(0) dinitrogen complex</title><title>Dalton transactions : an international journal of inorganic chemistry</title><addtitle>Dalton Trans</addtitle><description>The preparation and reactivity of a novel molybdenum dinitrogen complex supported by a nitrogen-centred tripodal phosphine ligand (N-triphos, N(CH
2
PPh
2
)
3
, NP
3
Ph
) are reported. Reaction of N-triphos with [MoX
3
(THF)
3
] (X = Cl, Br, I) gave the Mo(
iii
) complex [MoX
3
(κ
2
-NP
3
Ph
)(THF)] (
1
), where bidentate N-triphos coordination was observed. Reduction of this complex in the presence of dppm (bis(diphenylphosphino)methane) gave the dinitrogen complex [Mo(N
2
)(dppm)(κ
3
-NP
3
Ph
)] (
2
), which exhibits moderate dinitrogen activation. An additional hydride complex, [Mo(H)
2
(dppm)(κ
3
-NP
3
Ph
)] (
4
), was produced either as a minor side product during the reduction step, or as a major product by direct hydrogenation of the dinitrogen complex
2
. The reactivity of the dinitrogen complex
2
with a range of Lewis acids was also investigated. At low temperatures, protic or borane Lewis acids (H
+
, BBr
3
and tris(pentafluorophenyl)borane (BCF)) were found to coordinate to the apical nitrogen atom of the N-triphos ligand, with no conclusive evidence of any functionalisation of the dinitrogen ligand. Alkali metal Lewis acid addition to
2
resulted in the unexpected rearrangement of the N-triphos ligand to form [Mo(dppm)(PMePh
2
)(PCP)][B(C
6
F
5
)
4
] (
7
), where PCP, [Ph
2
PCNHCH
2
PPh
2
] is the carbenic ligand formed upon rearrangement from the reaction of
2
with M[B(C
6
F
5
)
4
] (M = Li, Na or K). Single crystal X-ray diffraction of complexes
1
,
2
,
4
and
7
provided structural confirmation of the N-triphos molybdenum complexes described.
N-Triphos/Mo(0)-dinitrogen reactivity: hydrogenation; Lewis acid addition; and alkali metal mediated ligand rearrangement.</description><subject>Alkali metals</subject><subject>Crystal structure</subject><subject>Lewis acid</subject><subject>Ligands</subject><subject>Molybdenum</subject><subject>Nitrogen compounds</subject><subject>Reactivity</subject><subject>Reduction</subject><subject>Single crystals</subject><subject>X-ray diffraction</subject><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2018</creationdate><recordtype>article</recordtype><recordid>eNpd0c9LwzAUB_AgitPpxbtS8DKFan42yXHM-QOmHpznkqWp62ibmaTi_nujmxM85fHeh8fjGwBOELxCkMhrLYoAMeXI7IADRDlPJSZ0d1vjrAcOvV9AiDFkeB_0CIRZJPgADF9WbZgbX_lEtUXijNKh-qjCKrFl7CRPaXDVcm598mgH8CIpqrYKzr6ZNtG2Wdbm8wjslar25njz9sHr7Xg6uk8nz3cPo-Ek1ZTIkErODC5FoYjiKpspxgwktNCSIaJowYgiAmHJOSlZVIISlXGkNY8XS6EM6YPBeu_S2ffO-JA3ldemrlVrbOdzDAUUWBJMIz3_Rxe2c228LioJWYZFJqK6XCvtrPfOlPnSVY1yqxzB_DvYfCRupj_BjiM-26zsZo0ptvQ3yQhO18B5vZ3-_Qz5AqkTeng</recordid><startdate>2018</startdate><enddate>2018</enddate><creator>Apps, Samantha L</creator><creator>White, Andrew J. P</creator><creator>Miller, Philip W</creator><creator>Long, Nicholas J</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/0000-0002-8394-2516</orcidid><orcidid>https://orcid.org/0000-0002-8298-938X</orcidid><orcidid>https://orcid.org/0000-0002-9970-5857</orcidid></search><sort><creationdate>2018</creationdate><title>Synthesis and reactivity of an N-triphos Mo(0) dinitrogen complex</title><author>Apps, Samantha L ; White, Andrew J. P ; Miller, Philip W ; Long, Nicholas J</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c439t-975e2f8da3a7a6ba55e034dc9513a4d53a38129773f58da843a671cc705298ae3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2018</creationdate><topic>Alkali metals</topic><topic>Crystal structure</topic><topic>Lewis acid</topic><topic>Ligands</topic><topic>Molybdenum</topic><topic>Nitrogen compounds</topic><topic>Reactivity</topic><topic>Reduction</topic><topic>Single crystals</topic><topic>X-ray diffraction</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Apps, Samantha L</creatorcontrib><creatorcontrib>White, Andrew J. P</creatorcontrib><creatorcontrib>Miller, Philip W</creatorcontrib><creatorcontrib>Long, Nicholas J</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>Apps, Samantha L</au><au>White, Andrew J. P</au><au>Miller, Philip W</au><au>Long, Nicholas J</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis and reactivity of an N-triphos Mo(0) dinitrogen complex</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>33</issue><spage>11386</spage><epage>11396</epage><pages>11386-11396</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract>The preparation and reactivity of a novel molybdenum dinitrogen complex supported by a nitrogen-centred tripodal phosphine ligand (N-triphos, N(CH
2
PPh
2
)
3
, NP
3
Ph
) are reported. Reaction of N-triphos with [MoX
3
(THF)
3
] (X = Cl, Br, I) gave the Mo(
iii
) complex [MoX
3
(κ
2
-NP
3
Ph
)(THF)] (
1
), where bidentate N-triphos coordination was observed. Reduction of this complex in the presence of dppm (bis(diphenylphosphino)methane) gave the dinitrogen complex [Mo(N
2
)(dppm)(κ
3
-NP
3
Ph
)] (
2
), which exhibits moderate dinitrogen activation. An additional hydride complex, [Mo(H)
2
(dppm)(κ
3
-NP
3
Ph
)] (
4
), was produced either as a minor side product during the reduction step, or as a major product by direct hydrogenation of the dinitrogen complex
2
. The reactivity of the dinitrogen complex
2
with a range of Lewis acids was also investigated. At low temperatures, protic or borane Lewis acids (H
+
, BBr
3
and tris(pentafluorophenyl)borane (BCF)) were found to coordinate to the apical nitrogen atom of the N-triphos ligand, with no conclusive evidence of any functionalisation of the dinitrogen ligand. Alkali metal Lewis acid addition to
2
resulted in the unexpected rearrangement of the N-triphos ligand to form [Mo(dppm)(PMePh
2
)(PCP)][B(C
6
F
5
)
4
] (
7
), where PCP, [Ph
2
PCNHCH
2
PPh
2
] is the carbenic ligand formed upon rearrangement from the reaction of
2
with M[B(C
6
F
5
)
4
] (M = Li, Na or K). Single crystal X-ray diffraction of complexes
1
,
2
,
4
and
7
provided structural confirmation of the N-triphos molybdenum complexes described.
N-Triphos/Mo(0)-dinitrogen reactivity: hydrogenation; Lewis acid addition; and alkali metal mediated ligand rearrangement.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>30062342</pmid><doi>10.1039/c8dt02471e</doi><tpages>11</tpages><orcidid>https://orcid.org/0000-0002-8394-2516</orcidid><orcidid>https://orcid.org/0000-0002-8298-938X</orcidid><orcidid>https://orcid.org/0000-0002-9970-5857</orcidid><oa>free_for_read</oa></addata></record> |
fulltext | fulltext |
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issn | 1477-9226 1477-9234 |
language | eng |
recordid | cdi_proquest_journals_2090562868 |
source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
subjects | Alkali metals Crystal structure Lewis acid Ligands Molybdenum Nitrogen compounds Reactivity Reduction Single crystals X-ray diffraction |
title | Synthesis and reactivity of an N-triphos Mo(0) dinitrogen complex |
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