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Influence of the Diphosphine Coordinated to Molybdenum and Tungsten Triangular M3S4 Cluster Hydrides in the Catalytic Hydrodefluorination of Pentafluoropyridine
Hydrido molybdenum and tungsten(IV) cluster cations of formula [M 3 S 4 H 3 (dppe) 3 ] + (dppe = 1,2-(bis)dimethylphosphinoethane), [ Mo-1 ] + (M = Mo) and [ W-1 ] + (M = W), have been isolated by reacting their halide precursors with borohydride. Synthetic procedures have been optimized by appropri...
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| Published in: | Journal of cluster science 2015-01, Vol.26 (1), p.199-209 |
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| creator | Alfonso, Carmina Beltrán, Tomás F. Feliz, Marta Llusar, Rosa |
| description | Hydrido molybdenum and tungsten(IV) cluster cations of formula [M
3
S
4
H
3
(dppe)
3
]
+
(dppe = 1,2-(bis)dimethylphosphinoethane), [
Mo-1
]
+
(M = Mo) and [
W-1
]
+
(M = W), have been isolated by reacting their halide precursors with borohydride. Synthetic procedures have been optimized by appropriate choice of the solvent. Furthermore, [M
3
S
4
F
3
(dppe)
3
]
+
fluorido cluster complexes, [
Mo-2
]
+
(M = Mo) and [
W-2
]
+
(M = W) have been prepared through halogen substitution reactions using an excess of cesium fluoride. The structures of [
Mo-1
]
+
and [
Mo-2
]
+
have been determined by single crystal X-ray diffraction experiments. These [
M-1
]
+
hydrido and [
M-2
]
+
fluorido clusters have been used as catalysts and precatalysts, respectively, in the catalytic hydrodefluorination (HDF) of pentafluoropyridine using HSiMe
2
Ph as hydrogen source. The reaction proceeds under microwave and reflux conditions to selectively afford 2,3,5,6-tetrafluoropyridine. The [
W-1
]
+
hydrido cluster is the most efficient catalyst with turnover numbers of 124, while the [
Mo-1
]
+
hydrido cluster reacts faster. Fluorido [
Mo-2
]
+
and [
W-2
]
+
complexes provide lower yields and turnover numbers. In general, the molybdenum and tungsten [
M-1
]
+
and [
M-2
]
+
diphosphino complexes are more efficient than their dmpe (1,2-(bis)dimethylphosphinoethano) analogues and activate pentafluoropyridine under softer conditions.
Graphical Abstract |
| doi_str_mv | 10.1007/s10876-014-0733-1 |
| format | article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_journals_2918290376</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2918290376</sourcerecordid><originalsourceid>FETCH-LOGICAL-c458t-8fdf3274ffacd0e5f412789b2acdcda0007e0ae508b24990f55f88e6e20db54a3</originalsourceid><addsrcrecordid>eNp1Ub1u2zAQFoIUaOLmAboR6KzmSEkmNQZqGxuwkQJ1ZoIWjzYNhVRJatDb9FFL2wU6ZTre8fu5w1cUnyl8pQD8MVIQfFkCrUvgVVXSm-KONpyVQizZbX5DDSVnXHws7mM8AUArququ-LN2ZpjQ9Ui8IemI5Jsdjz6OR-uQdN4HbZ1KqEnyZOuHea_RTW9EOU12kzvEhI7sglXuMA0qkG31qybdMOV5IKtZB6sxEusu0p1KapiT7S8_XmO29uGsb707-_9El9Rl6Mc5U_MOn4oPRg0RH_7VRfH64_uuW5Wbl-d197Qp-7oRqRRGm4rx2hjVa8DG1DQf2-5Zbnut8r0cQWEDYs_qtgXTNEYIXCIDvW9qVS2KL1fdMfjfE8YkT34KLltK1lLBWqj4MqPoFdUHH2NAI8dg31SYJQV5DkJeg5A5CHkOQtLMYVdOzFh3wPBf-X3SX50ij3I</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2918290376</pqid></control><display><type>article</type><title>Influence of the Diphosphine Coordinated to Molybdenum and Tungsten Triangular M3S4 Cluster Hydrides in the Catalytic Hydrodefluorination of Pentafluoropyridine</title><source>Springer Link</source><creator>Alfonso, Carmina ; Beltrán, Tomás F. ; Feliz, Marta ; Llusar, Rosa</creator><creatorcontrib>Alfonso, Carmina ; Beltrán, Tomás F. ; Feliz, Marta ; Llusar, Rosa</creatorcontrib><description>Hydrido molybdenum and tungsten(IV) cluster cations of formula [M
3
S
4
H
3
(dppe)
3
]
+
(dppe = 1,2-(bis)dimethylphosphinoethane), [
Mo-1
]
+
(M = Mo) and [
W-1
]
+
(M = W), have been isolated by reacting their halide precursors with borohydride. Synthetic procedures have been optimized by appropriate choice of the solvent. Furthermore, [M
3
S
4
F
3
(dppe)
3
]
+
fluorido cluster complexes, [
Mo-2
]
+
(M = Mo) and [
W-2
]
+
(M = W) have been prepared through halogen substitution reactions using an excess of cesium fluoride. The structures of [
Mo-1
]
+
and [
Mo-2
]
+
have been determined by single crystal X-ray diffraction experiments. These [
M-1
]
+
hydrido and [
M-2
]
+
fluorido clusters have been used as catalysts and precatalysts, respectively, in the catalytic hydrodefluorination (HDF) of pentafluoropyridine using HSiMe
2
Ph as hydrogen source. The reaction proceeds under microwave and reflux conditions to selectively afford 2,3,5,6-tetrafluoropyridine. The [
W-1
]
+
hydrido cluster is the most efficient catalyst with turnover numbers of 124, while the [
Mo-1
]
+
hydrido cluster reacts faster. Fluorido [
Mo-2
]
+
and [
W-2
]
+
complexes provide lower yields and turnover numbers. In general, the molybdenum and tungsten [
M-1
]
+
and [
M-2
]
+
diphosphino complexes are more efficient than their dmpe (1,2-(bis)dimethylphosphinoethano) analogues and activate pentafluoropyridine under softer conditions.
Graphical Abstract</description><identifier>ISSN: 1040-7278</identifier><identifier>EISSN: 1572-8862</identifier><identifier>DOI: 10.1007/s10876-014-0733-1</identifier><language>eng</language><publisher>Boston: Springer US</publisher><subject>Catalysis ; Catalysts ; Cesium fluorides ; Chemistry ; Chemistry and Materials Science ; Clusters ; Fluorides ; Fluorine ; Hydrogen ; Inorganic Chemistry ; Ligands ; Molybdenum ; Nanochemistry ; Nitrogen ; Original Paper ; Physical Chemistry ; Single crystals ; Solvents ; Substitution reactions ; Tungsten</subject><ispartof>Journal of cluster science, 2015-01, Vol.26 (1), p.199-209</ispartof><rights>Springer Science+Business Media New York 2014</rights><rights>Springer Science+Business Media New York 2014.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c458t-8fdf3274ffacd0e5f412789b2acdcda0007e0ae508b24990f55f88e6e20db54a3</citedby><cites>FETCH-LOGICAL-c458t-8fdf3274ffacd0e5f412789b2acdcda0007e0ae508b24990f55f88e6e20db54a3</cites></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></links><search><creatorcontrib>Alfonso, Carmina</creatorcontrib><creatorcontrib>Beltrán, Tomás F.</creatorcontrib><creatorcontrib>Feliz, Marta</creatorcontrib><creatorcontrib>Llusar, Rosa</creatorcontrib><title>Influence of the Diphosphine Coordinated to Molybdenum and Tungsten Triangular M3S4 Cluster Hydrides in the Catalytic Hydrodefluorination of Pentafluoropyridine</title><title>Journal of cluster science</title><addtitle>J Clust Sci</addtitle><description>Hydrido molybdenum and tungsten(IV) cluster cations of formula [M
3
S
4
H
3
(dppe)
3
]
+
(dppe = 1,2-(bis)dimethylphosphinoethane), [
Mo-1
]
+
(M = Mo) and [
W-1
]
+
(M = W), have been isolated by reacting their halide precursors with borohydride. Synthetic procedures have been optimized by appropriate choice of the solvent. Furthermore, [M
3
S
4
F
3
(dppe)
3
]
+
fluorido cluster complexes, [
Mo-2
]
+
(M = Mo) and [
W-2
]
+
(M = W) have been prepared through halogen substitution reactions using an excess of cesium fluoride. The structures of [
Mo-1
]
+
and [
Mo-2
]
+
have been determined by single crystal X-ray diffraction experiments. These [
M-1
]
+
hydrido and [
M-2
]
+
fluorido clusters have been used as catalysts and precatalysts, respectively, in the catalytic hydrodefluorination (HDF) of pentafluoropyridine using HSiMe
2
Ph as hydrogen source. The reaction proceeds under microwave and reflux conditions to selectively afford 2,3,5,6-tetrafluoropyridine. The [
W-1
]
+
hydrido cluster is the most efficient catalyst with turnover numbers of 124, while the [
Mo-1
]
+
hydrido cluster reacts faster. Fluorido [
Mo-2
]
+
and [
W-2
]
+
complexes provide lower yields and turnover numbers. In general, the molybdenum and tungsten [
M-1
]
+
and [
M-2
]
+
diphosphino complexes are more efficient than their dmpe (1,2-(bis)dimethylphosphinoethano) analogues and activate pentafluoropyridine under softer conditions.
Graphical Abstract</description><subject>Catalysis</subject><subject>Catalysts</subject><subject>Cesium fluorides</subject><subject>Chemistry</subject><subject>Chemistry and Materials Science</subject><subject>Clusters</subject><subject>Fluorides</subject><subject>Fluorine</subject><subject>Hydrogen</subject><subject>Inorganic Chemistry</subject><subject>Ligands</subject><subject>Molybdenum</subject><subject>Nanochemistry</subject><subject>Nitrogen</subject><subject>Original Paper</subject><subject>Physical Chemistry</subject><subject>Single crystals</subject><subject>Solvents</subject><subject>Substitution reactions</subject><subject>Tungsten</subject><issn>1040-7278</issn><issn>1572-8862</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><recordid>eNp1Ub1u2zAQFoIUaOLmAboR6KzmSEkmNQZqGxuwkQJ1ZoIWjzYNhVRJatDb9FFL2wU6ZTre8fu5w1cUnyl8pQD8MVIQfFkCrUvgVVXSm-KONpyVQizZbX5DDSVnXHws7mM8AUArququ-LN2ZpjQ9Ui8IemI5Jsdjz6OR-uQdN4HbZ1KqEnyZOuHea_RTW9EOU12kzvEhI7sglXuMA0qkG31qybdMOV5IKtZB6sxEusu0p1KapiT7S8_XmO29uGsb707-_9El9Rl6Mc5U_MOn4oPRg0RH_7VRfH64_uuW5Wbl-d197Qp-7oRqRRGm4rx2hjVa8DG1DQf2-5Zbnut8r0cQWEDYs_qtgXTNEYIXCIDvW9qVS2KL1fdMfjfE8YkT34KLltK1lLBWqj4MqPoFdUHH2NAI8dg31SYJQV5DkJeg5A5CHkOQtLMYVdOzFh3wPBf-X3SX50ij3I</recordid><startdate>20150101</startdate><enddate>20150101</enddate><creator>Alfonso, Carmina</creator><creator>Beltrán, Tomás F.</creator><creator>Feliz, Marta</creator><creator>Llusar, Rosa</creator><general>Springer US</general><general>Springer Nature B.V</general><scope>AAYXX</scope><scope>CITATION</scope><scope>3V.</scope><scope>7XB</scope><scope>88I</scope><scope>8FE</scope><scope>8FG</scope><scope>8FK</scope><scope>ABJCF</scope><scope>ABUWG</scope><scope>AFKRA</scope><scope>ARAPS</scope><scope>AZQEC</scope><scope>BENPR</scope><scope>BGLVJ</scope><scope>CCPQU</scope><scope>D1I</scope><scope>DWQXO</scope><scope>GNUQQ</scope><scope>HCIFZ</scope><scope>KB.</scope><scope>M2P</scope><scope>P5Z</scope><scope>P62</scope><scope>PDBOC</scope><scope>PQEST</scope><scope>PQQKQ</scope><scope>PQUKI</scope><scope>Q9U</scope></search><sort><creationdate>20150101</creationdate><title>Influence of the Diphosphine Coordinated to Molybdenum and Tungsten Triangular M3S4 Cluster Hydrides in the Catalytic Hydrodefluorination of Pentafluoropyridine</title><author>Alfonso, Carmina ; Beltrán, Tomás F. ; Feliz, Marta ; Llusar, Rosa</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c458t-8fdf3274ffacd0e5f412789b2acdcda0007e0ae508b24990f55f88e6e20db54a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><topic>Catalysis</topic><topic>Catalysts</topic><topic>Cesium fluorides</topic><topic>Chemistry</topic><topic>Chemistry and Materials Science</topic><topic>Clusters</topic><topic>Fluorides</topic><topic>Fluorine</topic><topic>Hydrogen</topic><topic>Inorganic Chemistry</topic><topic>Ligands</topic><topic>Molybdenum</topic><topic>Nanochemistry</topic><topic>Nitrogen</topic><topic>Original Paper</topic><topic>Physical Chemistry</topic><topic>Single crystals</topic><topic>Solvents</topic><topic>Substitution reactions</topic><topic>Tungsten</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Alfonso, Carmina</creatorcontrib><creatorcontrib>Beltrán, Tomás F.</creatorcontrib><creatorcontrib>Feliz, Marta</creatorcontrib><creatorcontrib>Llusar, Rosa</creatorcontrib><collection>CrossRef</collection><collection>ProQuest Central (Corporate)</collection><collection>ProQuest Central (purchase pre-March 2016)</collection><collection>Science Database (Alumni Edition)</collection><collection>ProQuest SciTech Collection</collection><collection>ProQuest Technology Collection</collection><collection>ProQuest Central (Alumni) (purchase pre-March 2016)</collection><collection>Materials Science & Engineering Collection</collection><collection>ProQuest Central (Alumni)</collection><collection>ProQuest Central</collection><collection>Advanced Technologies & Aerospace Collection</collection><collection>ProQuest Central Essentials</collection><collection>ProQuest Central</collection><collection>Technology Collection</collection><collection>ProQuest One Community College</collection><collection>ProQuest Materials Science Collection</collection><collection>ProQuest Central</collection><collection>ProQuest Central Student</collection><collection>SciTech Premium Collection</collection><collection>Materials Science Database</collection><collection>ProQuest Science Journals</collection><collection>Advanced Technologies & Aerospace Database</collection><collection>ProQuest Advanced Technologies & Aerospace Collection</collection><collection>Materials Science Collection</collection><collection>ProQuest One Academic Eastern Edition (DO NOT USE)</collection><collection>ProQuest One Academic</collection><collection>ProQuest One Academic UKI Edition</collection><collection>ProQuest Central Basic</collection><jtitle>Journal of cluster science</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Alfonso, Carmina</au><au>Beltrán, Tomás F.</au><au>Feliz, Marta</au><au>Llusar, Rosa</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Influence of the Diphosphine Coordinated to Molybdenum and Tungsten Triangular M3S4 Cluster Hydrides in the Catalytic Hydrodefluorination of Pentafluoropyridine</atitle><jtitle>Journal of cluster science</jtitle><stitle>J Clust Sci</stitle><date>2015-01-01</date><risdate>2015</risdate><volume>26</volume><issue>1</issue><spage>199</spage><epage>209</epage><pages>199-209</pages><issn>1040-7278</issn><eissn>1572-8862</eissn><abstract>Hydrido molybdenum and tungsten(IV) cluster cations of formula [M
3
S
4
H
3
(dppe)
3
]
+
(dppe = 1,2-(bis)dimethylphosphinoethane), [
Mo-1
]
+
(M = Mo) and [
W-1
]
+
(M = W), have been isolated by reacting their halide precursors with borohydride. Synthetic procedures have been optimized by appropriate choice of the solvent. Furthermore, [M
3
S
4
F
3
(dppe)
3
]
+
fluorido cluster complexes, [
Mo-2
]
+
(M = Mo) and [
W-2
]
+
(M = W) have been prepared through halogen substitution reactions using an excess of cesium fluoride. The structures of [
Mo-1
]
+
and [
Mo-2
]
+
have been determined by single crystal X-ray diffraction experiments. These [
M-1
]
+
hydrido and [
M-2
]
+
fluorido clusters have been used as catalysts and precatalysts, respectively, in the catalytic hydrodefluorination (HDF) of pentafluoropyridine using HSiMe
2
Ph as hydrogen source. The reaction proceeds under microwave and reflux conditions to selectively afford 2,3,5,6-tetrafluoropyridine. The [
W-1
]
+
hydrido cluster is the most efficient catalyst with turnover numbers of 124, while the [
Mo-1
]
+
hydrido cluster reacts faster. Fluorido [
Mo-2
]
+
and [
W-2
]
+
complexes provide lower yields and turnover numbers. In general, the molybdenum and tungsten [
M-1
]
+
and [
M-2
]
+
diphosphino complexes are more efficient than their dmpe (1,2-(bis)dimethylphosphinoethano) analogues and activate pentafluoropyridine under softer conditions.
Graphical Abstract</abstract><cop>Boston</cop><pub>Springer US</pub><doi>10.1007/s10876-014-0733-1</doi><tpages>11</tpages><oa>free_for_read</oa></addata></record> |
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| ispartof | Journal of cluster science, 2015-01, Vol.26 (1), p.199-209 |
| issn | 1040-7278 1572-8862 |
| language | eng |
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| source | Springer Link |
| subjects | Catalysis Catalysts Cesium fluorides Chemistry Chemistry and Materials Science Clusters Fluorides Fluorine Hydrogen Inorganic Chemistry Ligands Molybdenum Nanochemistry Nitrogen Original Paper Physical Chemistry Single crystals Solvents Substitution reactions Tungsten |
| title | Influence of the Diphosphine Coordinated to Molybdenum and Tungsten Triangular M3S4 Cluster Hydrides in the Catalytic Hydrodefluorination of Pentafluoropyridine |
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