Synthesis and characterization of dimeric μ‐oxidovanadium complexes as the functional model of vanadium bromoperoxidase
Two vanadium (IV) complexes [VIVO(Haeae‐sal)(MeOH)]+ (1) and [VIVO(Haeae‐hyap)(MeOH)]+ (2) were prepared by reacting [VO(acac)2] with ligands [H2aeae‐sal] (I) and [H2aeae‐hyap] (II) respectively. Condensation of 2‐(2‐aminoethylamino)ethanol with salicylaldehyde and 2‐hydroxyacetophenone produces the...
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| description | Two vanadium (IV) complexes [VIVO(Haeae‐sal)(MeOH)]+ (1) and [VIVO(Haeae‐hyap)(MeOH)]+ (2) were prepared by reacting [VO(acac)2] with ligands [H2aeae‐sal] (I) and [H2aeae‐hyap] (II) respectively. Condensation of 2‐(2‐aminoethylamino)ethanol with salicylaldehyde and 2‐hydroxyacetophenone produces the ligands (I) and (II) respectively. Both vanadium complexes 1 and 2 are sensitive towards aerial oxygen in solution and rapidly convert into vanadium(V) dioxido species. Vanadium(V) dioxido species crystalizes as the dimeric form in the solid‐state. Single‐crystal XRD analysis suggests octahedral geometry around each vanadium center in the solid‐state. To access the benefits of heterogeneous catalysis, vanadium(V) dioxido complexes were anchored into the polymeric chain of chloromethylated polystyrene. All the synthesized neat and supported vanadium complexes have been studied by a number of techniques to confirm their structural and functional properties. Bromoperoxidase activity of the synthesized vanadium(V) dioxido complexes 3 and 4 was examined by carrying out oxidative bromination of salicylaldehyde and oxidation of thioanisole. In the presence of hydrogen peroxide, 3 shows 94.4% conversion (TOF value of 2.739 × 102 h−1) and 4 exhibits 79.0% conversion (TOF value of 2.403 × 102 h−1) for the oxidative bromination of salicylaldehyde where 5‐bromosalicylaldehyde appears as the major product. Catalysts 3 and 4 also efficiently catalyze the oxidation of thioanisole in the presence of hydrogen peroxide where sulfoxide is observed as the major product. Covalent attachment of neat catalysts 3 and 4 into the polymer chain enhances substrate conversion (%) and their catalytic efficiency increases many folds, both in the oxidative bromination and oxidation of thioether. Polymer supported catalysts 5 displayed 98.8% conversion with a TOF value of 1.127 × 104 h−1 whereas catalyst 6 showed 95.7% conversion with a TOF value of 4.675 × 103 h−1 for the oxidative bromination of salicylaldehyde. These TOF values are the highest among the supported vanadium catalysts available in the literature for the oxidative bromination of salicylaldehyde.
Well‐characterized vanadium (V) oxido complexes were immobilized into the chloromethylated polystyrene beads and used as a potential catalyst for the oxidative bromination of salicylaldehyde. Easy separation, higher thermal stability, uncomplicated synthesis, and high efficiency make the supported catalysts an excellent choice for the o |
| doi_str_mv | 10.1002/aoc.5508 |
| format | Article |
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Well‐characterized vanadium (V) oxido complexes were immobilized into the chloromethylated polystyrene beads and used as a potential catalyst for the oxidative bromination of salicylaldehyde. Easy separation, higher thermal stability, uncomplicated synthesis, and high efficiency make the supported catalysts an excellent choice for the oxidative bromination of salicylaldehyde and oxidation of thioanisole among the recently reported heterogeneous catalysts.</description><identifier>ISSN: 0268-2605</identifier><identifier>EISSN: 1099-0739</identifier><identifier>DOI: 10.1002/aoc.5508</identifier><language>eng</language><publisher>Chichester: Wiley Subscription Services, Inc</publisher><subject>Bromination ; Catalysts ; Catalytic converters ; Chains (polymeric) ; Chemistry ; Condensates ; Conversion ; Dimers ; elemental mapping ; Ethanol ; heterogeneous catalysis ; Hydrogen peroxide ; Ligands ; Oxidation ; Polystyrene resins ; single crystal XRD ; Substrates ; Vanadium ; vanadium bromoperoxidase model ; μ‐oxidovanadium complexes</subject><ispartof>Applied organometallic chemistry, 2020-04, Vol.34 (4), p.n/a</ispartof><rights>2020 John Wiley & Sons, Ltd.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c2938-cdecedab87f7e07e8eac48bb16ecc00c5b29018a3c391c555b3d8ff80772e1763</citedby><cites>FETCH-LOGICAL-c2938-cdecedab87f7e07e8eac48bb16ecc00c5b29018a3c391c555b3d8ff80772e1763</cites><orcidid>0000-0003-4642-7918 ; 0000-0001-6977-9532</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Faoc.5508$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Faoc.5508$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids></links><search><creatorcontrib>Maurya, Abhishek</creatorcontrib><creatorcontrib>Mahato, Arun Kumar</creatorcontrib><creatorcontrib>Chaudhary, Nikita</creatorcontrib><creatorcontrib>Kesharwani, Neha</creatorcontrib><creatorcontrib>Kachhap, Payal</creatorcontrib><creatorcontrib>Mishra, Vivek Kumar</creatorcontrib><creatorcontrib>Haldar, Chanchal</creatorcontrib><title>Synthesis and characterization of dimeric μ‐oxidovanadium complexes as the functional model of vanadium bromoperoxidase</title><title>Applied organometallic chemistry</title><description>Two vanadium (IV) complexes [VIVO(Haeae‐sal)(MeOH)]+ (1) and [VIVO(Haeae‐hyap)(MeOH)]+ (2) were prepared by reacting [VO(acac)2] with ligands [H2aeae‐sal] (I) and [H2aeae‐hyap] (II) respectively. Condensation of 2‐(2‐aminoethylamino)ethanol with salicylaldehyde and 2‐hydroxyacetophenone produces the ligands (I) and (II) respectively. Both vanadium complexes 1 and 2 are sensitive towards aerial oxygen in solution and rapidly convert into vanadium(V) dioxido species. Vanadium(V) dioxido species crystalizes as the dimeric form in the solid‐state. Single‐crystal XRD analysis suggests octahedral geometry around each vanadium center in the solid‐state. To access the benefits of heterogeneous catalysis, vanadium(V) dioxido complexes were anchored into the polymeric chain of chloromethylated polystyrene. All the synthesized neat and supported vanadium complexes have been studied by a number of techniques to confirm their structural and functional properties. Bromoperoxidase activity of the synthesized vanadium(V) dioxido complexes 3 and 4 was examined by carrying out oxidative bromination of salicylaldehyde and oxidation of thioanisole. In the presence of hydrogen peroxide, 3 shows 94.4% conversion (TOF value of 2.739 × 102 h−1) and 4 exhibits 79.0% conversion (TOF value of 2.403 × 102 h−1) for the oxidative bromination of salicylaldehyde where 5‐bromosalicylaldehyde appears as the major product. Catalysts 3 and 4 also efficiently catalyze the oxidation of thioanisole in the presence of hydrogen peroxide where sulfoxide is observed as the major product. Covalent attachment of neat catalysts 3 and 4 into the polymer chain enhances substrate conversion (%) and their catalytic efficiency increases many folds, both in the oxidative bromination and oxidation of thioether. Polymer supported catalysts 5 displayed 98.8% conversion with a TOF value of 1.127 × 104 h−1 whereas catalyst 6 showed 95.7% conversion with a TOF value of 4.675 × 103 h−1 for the oxidative bromination of salicylaldehyde. These TOF values are the highest among the supported vanadium catalysts available in the literature for the oxidative bromination of salicylaldehyde.
Well‐characterized vanadium (V) oxido complexes were immobilized into the chloromethylated polystyrene beads and used as a potential catalyst for the oxidative bromination of salicylaldehyde. Easy separation, higher thermal stability, uncomplicated synthesis, and high efficiency make the supported catalysts an excellent choice for the oxidative bromination of salicylaldehyde and oxidation of thioanisole among the recently reported heterogeneous catalysts.</description><subject>Bromination</subject><subject>Catalysts</subject><subject>Catalytic converters</subject><subject>Chains (polymeric)</subject><subject>Chemistry</subject><subject>Condensates</subject><subject>Conversion</subject><subject>Dimers</subject><subject>elemental mapping</subject><subject>Ethanol</subject><subject>heterogeneous catalysis</subject><subject>Hydrogen peroxide</subject><subject>Ligands</subject><subject>Oxidation</subject><subject>Polystyrene resins</subject><subject>single crystal XRD</subject><subject>Substrates</subject><subject>Vanadium</subject><subject>vanadium bromoperoxidase model</subject><subject>μ‐oxidovanadium complexes</subject><issn>0268-2605</issn><issn>1099-0739</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><recordid>eNp10E9KxDAUBvAgCo6j4BECbtx0fGmmTbocBv_BwCzUdUmTV6ZD29Sk1ZlZeQQP5Bk8hCexdcSdq_Dg932Ej5BzBhMGEF4pqydRBPKAjBgkSQCCJ4dkBGEsgzCG6JiceL8GgCRm0xHZPWzrdoW-8FTVhuqVckq36IqdagtbU5tTU1T9rennx9fbu90Uxr6oWpmiq6i2VVPiBvuwp30NzbtaDzlV0soaLIf8n86crWyDbuhQHk_JUa5Kj2e_75g83Vw_zu-CxfL2fj5bBDpMuAy0QY1GZVLkAkGgRKWnMstYjFoD6CgLE2BScc0TpqMoyriReS5BiBCZiPmYXOx7G2efO_Rturad67_o05CLGAQLOe_V5V5pZ713mKeNKyrltimDdFg27ZdNh2V7Guzpa1Hi9l-XzpbzH_8NU39_DA</recordid><startdate>202004</startdate><enddate>202004</enddate><creator>Maurya, Abhishek</creator><creator>Mahato, Arun Kumar</creator><creator>Chaudhary, Nikita</creator><creator>Kesharwani, Neha</creator><creator>Kachhap, Payal</creator><creator>Mishra, Vivek Kumar</creator><creator>Haldar, Chanchal</creator><general>Wiley Subscription Services, Inc</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope><orcidid>https://orcid.org/0000-0003-4642-7918</orcidid><orcidid>https://orcid.org/0000-0001-6977-9532</orcidid></search><sort><creationdate>202004</creationdate><title>Synthesis and characterization of dimeric μ‐oxidovanadium complexes as the functional model of vanadium bromoperoxidase</title><author>Maurya, Abhishek ; Mahato, Arun Kumar ; Chaudhary, Nikita ; Kesharwani, Neha ; Kachhap, Payal ; Mishra, Vivek Kumar ; Haldar, Chanchal</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c2938-cdecedab87f7e07e8eac48bb16ecc00c5b29018a3c391c555b3d8ff80772e1763</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>Bromination</topic><topic>Catalysts</topic><topic>Catalytic converters</topic><topic>Chains (polymeric)</topic><topic>Chemistry</topic><topic>Condensates</topic><topic>Conversion</topic><topic>Dimers</topic><topic>elemental mapping</topic><topic>Ethanol</topic><topic>heterogeneous catalysis</topic><topic>Hydrogen peroxide</topic><topic>Ligands</topic><topic>Oxidation</topic><topic>Polystyrene resins</topic><topic>single crystal XRD</topic><topic>Substrates</topic><topic>Vanadium</topic><topic>vanadium bromoperoxidase model</topic><topic>μ‐oxidovanadium complexes</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Maurya, Abhishek</creatorcontrib><creatorcontrib>Mahato, Arun Kumar</creatorcontrib><creatorcontrib>Chaudhary, Nikita</creatorcontrib><creatorcontrib>Kesharwani, Neha</creatorcontrib><creatorcontrib>Kachhap, Payal</creatorcontrib><creatorcontrib>Mishra, Vivek Kumar</creatorcontrib><creatorcontrib>Haldar, Chanchal</creatorcontrib><collection>CrossRef</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><jtitle>Applied organometallic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Maurya, Abhishek</au><au>Mahato, Arun Kumar</au><au>Chaudhary, Nikita</au><au>Kesharwani, Neha</au><au>Kachhap, Payal</au><au>Mishra, Vivek Kumar</au><au>Haldar, Chanchal</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis and characterization of dimeric μ‐oxidovanadium complexes as the functional model of vanadium bromoperoxidase</atitle><jtitle>Applied organometallic chemistry</jtitle><date>2020-04</date><risdate>2020</risdate><volume>34</volume><issue>4</issue><epage>n/a</epage><issn>0268-2605</issn><eissn>1099-0739</eissn><abstract>Two vanadium (IV) complexes [VIVO(Haeae‐sal)(MeOH)]+ (1) and [VIVO(Haeae‐hyap)(MeOH)]+ (2) were prepared by reacting [VO(acac)2] with ligands [H2aeae‐sal] (I) and [H2aeae‐hyap] (II) respectively. Condensation of 2‐(2‐aminoethylamino)ethanol with salicylaldehyde and 2‐hydroxyacetophenone produces the ligands (I) and (II) respectively. Both vanadium complexes 1 and 2 are sensitive towards aerial oxygen in solution and rapidly convert into vanadium(V) dioxido species. Vanadium(V) dioxido species crystalizes as the dimeric form in the solid‐state. Single‐crystal XRD analysis suggests octahedral geometry around each vanadium center in the solid‐state. To access the benefits of heterogeneous catalysis, vanadium(V) dioxido complexes were anchored into the polymeric chain of chloromethylated polystyrene. All the synthesized neat and supported vanadium complexes have been studied by a number of techniques to confirm their structural and functional properties. Bromoperoxidase activity of the synthesized vanadium(V) dioxido complexes 3 and 4 was examined by carrying out oxidative bromination of salicylaldehyde and oxidation of thioanisole. In the presence of hydrogen peroxide, 3 shows 94.4% conversion (TOF value of 2.739 × 102 h−1) and 4 exhibits 79.0% conversion (TOF value of 2.403 × 102 h−1) for the oxidative bromination of salicylaldehyde where 5‐bromosalicylaldehyde appears as the major product. Catalysts 3 and 4 also efficiently catalyze the oxidation of thioanisole in the presence of hydrogen peroxide where sulfoxide is observed as the major product. Covalent attachment of neat catalysts 3 and 4 into the polymer chain enhances substrate conversion (%) and their catalytic efficiency increases many folds, both in the oxidative bromination and oxidation of thioether. Polymer supported catalysts 5 displayed 98.8% conversion with a TOF value of 1.127 × 104 h−1 whereas catalyst 6 showed 95.7% conversion with a TOF value of 4.675 × 103 h−1 for the oxidative bromination of salicylaldehyde. These TOF values are the highest among the supported vanadium catalysts available in the literature for the oxidative bromination of salicylaldehyde.
Well‐characterized vanadium (V) oxido complexes were immobilized into the chloromethylated polystyrene beads and used as a potential catalyst for the oxidative bromination of salicylaldehyde. Easy separation, higher thermal stability, uncomplicated synthesis, and high efficiency make the supported catalysts an excellent choice for the oxidative bromination of salicylaldehyde and oxidation of thioanisole among the recently reported heterogeneous catalysts.</abstract><cop>Chichester</cop><pub>Wiley Subscription Services, Inc</pub><doi>10.1002/aoc.5508</doi><tpages>21</tpages><orcidid>https://orcid.org/0000-0003-4642-7918</orcidid><orcidid>https://orcid.org/0000-0001-6977-9532</orcidid></addata></record> |
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| subjects | Bromination Catalysts Catalytic converters Chains (polymeric) Chemistry Condensates Conversion Dimers elemental mapping Ethanol heterogeneous catalysis Hydrogen peroxide Ligands Oxidation Polystyrene resins single crystal XRD Substrates Vanadium vanadium bromoperoxidase model μ‐oxidovanadium complexes |
| title | Synthesis and characterization of dimeric μ‐oxidovanadium complexes as the functional model of vanadium bromoperoxidase |
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