Non-oxo vanadium(IV) alkoxide chemistry: solid state structures, aggregation equilibria and thermochromic behaviour in solution
The reversible thermochromic behaviour of homoleptic [{V(OR)(4)}(n)] complexes in solution [R = Pr(i) (product I), Bu(s) (B(s)), Nep (N) and Cy (C)] is accounted for the existence of an aggregation equilibrium involving dimeric and monomeric species in which vanadium(iv) is respectively five- and fo...
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| Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2011-04, Vol.40 (13), p.3198-3210 |
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| container_title | Dalton transactions : an international journal of inorganic chemistry |
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| creator | Westrup, Kátia C M Gregório, Thaiane Stinghen, Danilo Reis, Dayane M Hitchcock, Peter B Ribeiro, Ronny R Barison, Andersson Back, Davi F de Sá, Eduardo L Nunes, Giovana G Soares, Jaísa F |
| description | The reversible thermochromic behaviour of homoleptic [{V(OR)(4)}(n)] complexes in solution [R = Pr(i) (product I), Bu(s) (B(s)), Nep (N) and Cy (C)] is accounted for the existence of an aggregation equilibrium involving dimeric and monomeric species in which vanadium(iv) is respectively five- and four-coordinate. Bulky R groups such as Bu(t) and Pe(t) (tert-pentoxide) prevent aggregation and therefore give rise to exclusively mononuclear compounds (B(t) and P(t), respectively) that are not thermochromic. The complexes and their temperature-dependent interconversion were characterised by single crystal X-ray diffractometry, magnetic susceptibility measurements and electronic, FTIR and EPR spectroscopies in a wide temperature range. Equilibrium constants and enthalpy and entropy changes for the dimerization reactions have been determined and compared with literature data. |
| doi_str_mv | 10.1039/c0dt01547d |
| format | Article |
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Bulky R groups such as Bu(t) and Pe(t) (tert-pentoxide) prevent aggregation and therefore give rise to exclusively mononuclear compounds (B(t) and P(t), respectively) that are not thermochromic. The complexes and their temperature-dependent interconversion were characterised by single crystal X-ray diffractometry, magnetic susceptibility measurements and electronic, FTIR and EPR spectroscopies in a wide temperature range. Equilibrium constants and enthalpy and entropy changes for the dimerization reactions have been determined and compared with literature data.</description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/c0dt01547d</identifier><identifier>PMID: 21347465</identifier><language>eng</language><publisher>England</publisher><subject>Agglomeration ; Buses (vehicles) ; Chemical equilibrium ; Diffraction ; Dimerization ; Electronics ; Entropy ; Magnetic permeability</subject><ispartof>Dalton transactions : an international journal of inorganic chemistry, 2011-04, Vol.40 (13), p.3198-3210</ispartof><rights>The Royal Society of Chemistry 2011</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c352t-9c414d44426967eee0f148729d8444828913b93dadcca4a731e68497c6b146483</citedby><cites>FETCH-LOGICAL-c352t-9c414d44426967eee0f148729d8444828913b93dadcca4a731e68497c6b146483</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27901,27902</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/21347465$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Westrup, Kátia C M</creatorcontrib><creatorcontrib>Gregório, Thaiane</creatorcontrib><creatorcontrib>Stinghen, Danilo</creatorcontrib><creatorcontrib>Reis, Dayane M</creatorcontrib><creatorcontrib>Hitchcock, Peter B</creatorcontrib><creatorcontrib>Ribeiro, Ronny R</creatorcontrib><creatorcontrib>Barison, Andersson</creatorcontrib><creatorcontrib>Back, Davi F</creatorcontrib><creatorcontrib>de Sá, Eduardo L</creatorcontrib><creatorcontrib>Nunes, Giovana G</creatorcontrib><creatorcontrib>Soares, Jaísa F</creatorcontrib><title>Non-oxo vanadium(IV) alkoxide chemistry: solid state structures, aggregation equilibria and thermochromic behaviour in solution</title><title>Dalton transactions : an international journal of inorganic chemistry</title><addtitle>Dalton Trans</addtitle><description>The reversible thermochromic behaviour of homoleptic [{V(OR)(4)}(n)] complexes in solution [R = Pr(i) (product I), Bu(s) (B(s)), Nep (N) and Cy (C)] is accounted for the existence of an aggregation equilibrium involving dimeric and monomeric species in which vanadium(iv) is respectively five- and four-coordinate. Bulky R groups such as Bu(t) and Pe(t) (tert-pentoxide) prevent aggregation and therefore give rise to exclusively mononuclear compounds (B(t) and P(t), respectively) that are not thermochromic. The complexes and their temperature-dependent interconversion were characterised by single crystal X-ray diffractometry, magnetic susceptibility measurements and electronic, FTIR and EPR spectroscopies in a wide temperature range. Equilibrium constants and enthalpy and entropy changes for the dimerization reactions have been determined and compared with literature data.</description><subject>Agglomeration</subject><subject>Buses (vehicles)</subject><subject>Chemical equilibrium</subject><subject>Diffraction</subject><subject>Dimerization</subject><subject>Electronics</subject><subject>Entropy</subject><subject>Magnetic permeability</subject><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2011</creationdate><recordtype>article</recordtype><recordid>eNqFkUlPHDEQRq0oKGy55AdEvgUiGry17eaGUBKQRskFuLbcds2Mk-4242UEJ_46PWLJDS4uq_TqSVUfQl8oOaaENyeWuExoLZT7gHaoUKpqGBcfX_9MbqPdlP4Swhip2Se0zSgXSsh6Bz38DmMV7gJem9E4X4aDy5tDbPp_4c47wHYJg0853p_iFHrvcMomw_TGYnOJkI6wWSwiLEz2YcSwKr73XfQGm9HhvIQ4BLuMYfAWd7A0ax9KxH7c2MpmZB9tzU2f4PNz3UPXP39cnV9Usz-_Ls_PZpXlNctVYwUVTgjBZCMVAJA5FVqxxumpqZluKO8a7oyz1gijOAWpRaOs7KiQQvM99O3JexvDqkDK7bSXhb43I4SSWl1PEqZ5PZEHb5JUcUKkkpK-jzJGtZLT2Sf0-xNqY0gpwry9jX4w8b6lpN2k2P5PcYK_PntLN4B7RV9i44_5Lpiu</recordid><startdate>20110407</startdate><enddate>20110407</enddate><creator>Westrup, Kátia C M</creator><creator>Gregório, Thaiane</creator><creator>Stinghen, Danilo</creator><creator>Reis, Dayane M</creator><creator>Hitchcock, Peter B</creator><creator>Ribeiro, Ronny R</creator><creator>Barison, Andersson</creator><creator>Back, Davi F</creator><creator>de Sá, Eduardo L</creator><creator>Nunes, Giovana G</creator><creator>Soares, Jaísa F</creator><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SP</scope><scope>7U5</scope><scope>8FD</scope><scope>L7M</scope><scope>7SR</scope><scope>8BQ</scope><scope>JG9</scope><scope>7X8</scope></search><sort><creationdate>20110407</creationdate><title>Non-oxo vanadium(IV) alkoxide chemistry: solid state structures, aggregation equilibria and thermochromic behaviour in solution</title><author>Westrup, Kátia C M ; 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| identifier | ISSN: 1477-9226 |
| ispartof | Dalton transactions : an international journal of inorganic chemistry, 2011-04, Vol.40 (13), p.3198-3210 |
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| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Agglomeration Buses (vehicles) Chemical equilibrium Diffraction Dimerization Electronics Entropy Magnetic permeability |
| title | Non-oxo vanadium(IV) alkoxide chemistry: solid state structures, aggregation equilibria and thermochromic behaviour in solution |
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