Hydrogenation of nickel and vanadyl tetraphenylporphyrin in absence of a catalyst: A kinetic study
The hydrodemetallation (HDM) reactions of nickel-5,10,15,20-tetraphenylporphyrin (Ni-TPP) and vanadyl-5,10,15,20-tetraphenylporphyrin (VO-TPP) were studied in the absence of a catalyst. Ni-TPP as well as VO-TPP is found to demetallate through a reversible sequential reaction mechanism in which simil...
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| Veröffentlicht in: | Applied catalysis. A, General General, 2001-01, Vol.206 (2), p.171-181 |
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| container_title | Applied catalysis. A, General |
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| creator | Bonné, R.L.C van Steenderen, P Moulijn, J.A |
| description | The hydrodemetallation (HDM) reactions of nickel-5,10,15,20-tetraphenylporphyrin (Ni-TPP) and vanadyl-5,10,15,20-tetraphenylporphyrin (VO-TPP) were studied in the absence of a catalyst.
Ni-TPP as well as VO-TPP is found to demetallate through a reversible sequential reaction mechanism in which similar hydrogenated intermediate species are formed. As compared to catalized HDM, reaction rates are low. Hydrogenation reactions of Ni-TPP are first order with respect to the liquid phase concentration of hydrogen. Hydrogen sulfide promotes the conversion of Ni-TPP. An equilibrium constant for the reversible hydrogenation of Ni-TPP to nickel-5,10,15,20-tetraphenylchlorin (Ni-TPC) has been estimated as a function of temperature. A heat of reaction of −97
kJ/mol was found for the reversible hydrogenation of Ni-TPP to Ni-TPC.
Comparison of the reactivities of a metal-free porphyrin (H
2-TPP), Ni-TPP and VO-TPP revealed that the metals have a stabilizing influence towards hydrogenation and ring fragmentation of porphyrin macrocycles. |
| doi_str_mv | 10.1016/S0926-860X(00)00587-1 |
| format | Article |
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Ni-TPP as well as VO-TPP is found to demetallate through a reversible sequential reaction mechanism in which similar hydrogenated intermediate species are formed. As compared to catalized HDM, reaction rates are low. Hydrogenation reactions of Ni-TPP are first order with respect to the liquid phase concentration of hydrogen. Hydrogen sulfide promotes the conversion of Ni-TPP. An equilibrium constant for the reversible hydrogenation of Ni-TPP to nickel-5,10,15,20-tetraphenylchlorin (Ni-TPC) has been estimated as a function of temperature. A heat of reaction of −97
kJ/mol was found for the reversible hydrogenation of Ni-TPP to Ni-TPC.
Comparison of the reactivities of a metal-free porphyrin (H
2-TPP), Ni-TPP and VO-TPP revealed that the metals have a stabilizing influence towards hydrogenation and ring fragmentation of porphyrin macrocycles.</description><identifier>ISSN: 0926-860X</identifier><identifier>EISSN: 1873-3875</identifier><identifier>DOI: 10.1016/S0926-860X(00)00587-1</identifier><language>eng</language><publisher>Amsterdam: Elsevier B.V</publisher><subject>Catalysis ; Catalyst ; Catalysts: preparations and properties ; Chemistry ; Exact sciences and technology ; General and physical chemistry ; Hydrogenation ; Nickel tetraphenylporphyrin ; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry ; Vanadyl tetraphenylporphyrin</subject><ispartof>Applied catalysis. A, General, 2001-01, Vol.206 (2), p.171-181</ispartof><rights>2001 Elsevier Science B.V.</rights><rights>2001 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://www.sciencedirect.com/science/article/pii/S0926860X00005871$$EHTML$$P50$$Gelsevier$$H</linktohtml><link.rule.ids>314,776,780,3537,27901,27902,65306</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=829576$$DView record in Pascal Francis$$Hfree_for_read</backlink></links><search><creatorcontrib>Bonné, R.L.C</creatorcontrib><creatorcontrib>van Steenderen, P</creatorcontrib><creatorcontrib>Moulijn, J.A</creatorcontrib><title>Hydrogenation of nickel and vanadyl tetraphenylporphyrin in absence of a catalyst: A kinetic study</title><title>Applied catalysis. A, General</title><description>The hydrodemetallation (HDM) reactions of nickel-5,10,15,20-tetraphenylporphyrin (Ni-TPP) and vanadyl-5,10,15,20-tetraphenylporphyrin (VO-TPP) were studied in the absence of a catalyst.
Ni-TPP as well as VO-TPP is found to demetallate through a reversible sequential reaction mechanism in which similar hydrogenated intermediate species are formed. As compared to catalized HDM, reaction rates are low. Hydrogenation reactions of Ni-TPP are first order with respect to the liquid phase concentration of hydrogen. Hydrogen sulfide promotes the conversion of Ni-TPP. An equilibrium constant for the reversible hydrogenation of Ni-TPP to nickel-5,10,15,20-tetraphenylchlorin (Ni-TPC) has been estimated as a function of temperature. A heat of reaction of −97
kJ/mol was found for the reversible hydrogenation of Ni-TPP to Ni-TPC.
Comparison of the reactivities of a metal-free porphyrin (H
2-TPP), Ni-TPP and VO-TPP revealed that the metals have a stabilizing influence towards hydrogenation and ring fragmentation of porphyrin macrocycles.</description><subject>Catalysis</subject><subject>Catalyst</subject><subject>Catalysts: preparations and properties</subject><subject>Chemistry</subject><subject>Exact sciences and technology</subject><subject>General and physical chemistry</subject><subject>Hydrogenation</subject><subject>Nickel tetraphenylporphyrin</subject><subject>Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry</subject><subject>Vanadyl tetraphenylporphyrin</subject><issn>0926-860X</issn><issn>1873-3875</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2001</creationdate><recordtype>article</recordtype><recordid>eNo9kE1LAzEQhoMoWKs_QQh40cNqsh_JxouU4hcUPKjgLUyTWRu7ZpckFvbfu21FGHgvzzvMPIScc3bNGRc3r0zlIqsF-7hk7IqxqpYZPyATXssiK2pZHZLJP3JMTmL8YozlpaomZPk02NB9oofkOk-7hnpn1thS8JZuwIMdWpowBehX6Ie270K_GoLzdBxYRvQGty2gBhK0Q0y3dEbXzmNyhsb0Y4dTctRAG_HsL6fk_eH-bf6ULV4en-ezRYZ5IVNmRSULqZgoaqyMtNDUCCy3qjQlSi5sJYpSiTER0dRLRMgbKW0ppcwbpYopudjv7SEaaJsA3rio--C-IQy6zlUlxUjd7SkcT9k4DDoat_3CuoAmads5zZneitU7sXprTTOmd2I1L34BamVuaA</recordid><startdate>20010122</startdate><enddate>20010122</enddate><creator>Bonné, R.L.C</creator><creator>van Steenderen, P</creator><creator>Moulijn, J.A</creator><general>Elsevier B.V</general><general>Elsevier</general><scope>IQODW</scope></search><sort><creationdate>20010122</creationdate><title>Hydrogenation of nickel and vanadyl tetraphenylporphyrin in absence of a catalyst: A kinetic study</title><author>Bonné, R.L.C ; van Steenderen, P ; Moulijn, J.A</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-e237t-d6573790638e5c7daf8ea02d94c4e716d5634966d5eeec8beea2f77d47772f993</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2001</creationdate><topic>Catalysis</topic><topic>Catalyst</topic><topic>Catalysts: preparations and properties</topic><topic>Chemistry</topic><topic>Exact sciences and technology</topic><topic>General and physical chemistry</topic><topic>Hydrogenation</topic><topic>Nickel tetraphenylporphyrin</topic><topic>Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry</topic><topic>Vanadyl tetraphenylporphyrin</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Bonné, R.L.C</creatorcontrib><creatorcontrib>van Steenderen, P</creatorcontrib><creatorcontrib>Moulijn, J.A</creatorcontrib><collection>Pascal-Francis</collection><jtitle>Applied catalysis. A, General</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Bonné, R.L.C</au><au>van Steenderen, P</au><au>Moulijn, J.A</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Hydrogenation of nickel and vanadyl tetraphenylporphyrin in absence of a catalyst: A kinetic study</atitle><jtitle>Applied catalysis. A, General</jtitle><date>2001-01-22</date><risdate>2001</risdate><volume>206</volume><issue>2</issue><spage>171</spage><epage>181</epage><pages>171-181</pages><issn>0926-860X</issn><eissn>1873-3875</eissn><abstract>The hydrodemetallation (HDM) reactions of nickel-5,10,15,20-tetraphenylporphyrin (Ni-TPP) and vanadyl-5,10,15,20-tetraphenylporphyrin (VO-TPP) were studied in the absence of a catalyst.
Ni-TPP as well as VO-TPP is found to demetallate through a reversible sequential reaction mechanism in which similar hydrogenated intermediate species are formed. As compared to catalized HDM, reaction rates are low. Hydrogenation reactions of Ni-TPP are first order with respect to the liquid phase concentration of hydrogen. Hydrogen sulfide promotes the conversion of Ni-TPP. An equilibrium constant for the reversible hydrogenation of Ni-TPP to nickel-5,10,15,20-tetraphenylchlorin (Ni-TPC) has been estimated as a function of temperature. A heat of reaction of −97
kJ/mol was found for the reversible hydrogenation of Ni-TPP to Ni-TPC.
Comparison of the reactivities of a metal-free porphyrin (H
2-TPP), Ni-TPP and VO-TPP revealed that the metals have a stabilizing influence towards hydrogenation and ring fragmentation of porphyrin macrocycles.</abstract><cop>Amsterdam</cop><pub>Elsevier B.V</pub><doi>10.1016/S0926-860X(00)00587-1</doi><tpages>11</tpages></addata></record> |
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| identifier | ISSN: 0926-860X |
| ispartof | Applied catalysis. A, General, 2001-01, Vol.206 (2), p.171-181 |
| issn | 0926-860X 1873-3875 |
| language | eng |
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| source | Elsevier ScienceDirect Journals |
| subjects | Catalysis Catalyst Catalysts: preparations and properties Chemistry Exact sciences and technology General and physical chemistry Hydrogenation Nickel tetraphenylporphyrin Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry Vanadyl tetraphenylporphyrin |
| title | Hydrogenation of nickel and vanadyl tetraphenylporphyrin in absence of a catalyst: A kinetic study |
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