Vanadium(IV and V) Complexes Containing SNO (Dithiocarbonylhydrazone; Thiosemicarbazone) Donor Sets
Identifieur interne : 001461 ( Istex/Corpus ); précédent : 001460; suivant : 001462Vanadium(IV and V) Complexes Containing SNO (Dithiocarbonylhydrazone; Thiosemicarbazone) Donor Sets
Auteurs : Dongren Wang ; Martin Ebel ; Carola Schulzke ; Cerstin Grüning ; Saroj K. S. Hazari ; Dieter RehderSource :
- European Journal of Inorganic Chemistry [ 1434-1948 ] ; 2001-04.
English descriptors
- Teeft :
- Analogous manner, Axial position, Bathochromic shift, Bond angles, Bond lengths, Calcd, Chem, Condensation product, Dalton trans, Ethanol, Full paper, Green solution, Hydrazine hydrate, Hydrogen atoms, Imine nitrogen atom, Inorg, Intensity ratio, Latter case, Ligand, Main component, Mmol, Oxovanadium sulfate pentahydrate, Probability level, Rehder, Room temp, Room temperature, Sodium acetate trihydrate, Spectroscopic data, Sulfur, Sulfur coordination, Sulfur function, Tetragonal pyramid, Thiosemicarbazone, Transition metal, Tridentate ligand, Trigonal bipyramid, Vanadium, Vanadium centre, Vanadium complexes, Vanadyl sulfate.
Abstract
The VO2+ complexes [VOCl(ONS)] (3) and [VO(ONS)′] (4), and the VO3+ complexes [VO(OEt)(ONS)′] (5) {ONS = (R)‐salicylaldehyde thiosemicarbazonate(1−) R = 5,6‐C4H4 (3a) or 3‐OMe (3b); (ONS)′ = (R)‐salicylaldehyde[benzylmercaptothiocarbonylhydrazonate(2−)], R = H, (4a/5a) or 3‐OMe (4b/5b)} have been prepared and characterised by IR, EPR, 1H‐, and 51V‐NMR spectroscopy. In (S)‐sBuOH, 4a converts to [VO{(S)‐OsBu}(ONS)′] (5c) and [VO(OH)(ONS)′] (or a condensation product thereof). Solutions of 5c show three 51V NMR signals, two of which are due to two diastereomers. The EPR spectra of 3 and 4 in THF reveal the presence of octahedral species in solution. The crystal and molecular structures of complexes 3a·OCMe2, 5a, and 5b have been obtained, revealing basically a tetragonal pyramid, and coordination of the sulfur function in the thiocarbonyl (3) or enethiolate mode (5). The relevance of the compounds to bioinorganic aspects is addressed.
Url:
DOI: 10.1002/1099-0682(200104)2001:4<935::AID-EJIC935>3.0.CO;2-J
Links to Exploration step
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<front><div type="abstract" xml:lang="en">The VO2+ complexes [VOCl(ONS)] (3) and [VO(ONS)′] (4), and the VO3+ complexes [VO(OEt)(ONS)′] (5) {ONS = (R)‐salicylaldehyde thiosemicarbazonate(1−) R = 5,6‐C4H4 (3a) or 3‐OMe (3b); (ONS)′ = (R)‐salicylaldehyde[benzylmercaptothiocarbonylhydrazonate(2−)], R = H, (4a/5a) or 3‐OMe (4b/5b)} have been prepared and characterised by IR, EPR, 1H‐, and 51V‐NMR spectroscopy. In (S)‐sBuOH, 4a converts to [VO{(S)‐OsBu}(ONS)′] (5c) and [VO(OH)(ONS)′] (or a condensation product thereof). Solutions of 5c show three 51V NMR signals, two of which are due to two diastereomers. The EPR spectra of 3 and 4 in THF reveal the presence of octahedral species in solution. The crystal and molecular structures of complexes 3a·OCMe2, 5a, and 5b have been obtained, revealing basically a tetragonal pyramid, and coordination of the sulfur function in the thiocarbonyl (3) or enethiolate mode (5). The relevance of the compounds to bioinorganic aspects is addressed.</div>
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<abstract>The VO2+ complexes [VOCl(ONS)] (3) and [VO(ONS)′] (4), and the VO3+ complexes [VO(OEt)(ONS)′] (5) {ONS = (R)‐salicylaldehyde thiosemicarbazonate(1−) R = 5,6‐C4H4 (3a) or 3‐OMe (3b); (ONS)′ = (R)‐salicylaldehyde[benzylmercaptothiocarbonylhydrazonate(2−)], R = H, (4a/5a) or 3‐OMe (4b/5b)} have been prepared and characterised by IR, EPR, 1H‐, and 51V‐NMR spectroscopy. In (S)‐sBuOH, 4a converts to [VO{(S)‐OsBu}(ONS)′] (5c) and [VO(OH)(ONS)′] (or a condensation product thereof). Solutions of 5c show three 51V NMR signals, two of which are due to two diastereomers. The EPR spectra of 3 and 4 in THF reveal the presence of octahedral species in solution. The crystal and molecular structures of complexes 3a·OCMe2, 5a, and 5b have been obtained, revealing basically a tetragonal pyramid, and coordination of the sulfur function in the thiocarbonyl (3) or enethiolate mode (5). The relevance of the compounds to bioinorganic aspects is addressed.</abstract>
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<profileDesc><abstract xml:lang="en" style="main"><head>Abstract</head>
<p>The VO<hi rend="superscript">2+</hi>
complexes [VOCl(<hi rend="italic">ONS</hi>
)] (<hi rend="bold">3</hi>
) and [VO(<hi rend="italic">ONS</hi>
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complexes [VO(OEt)(<hi rend="italic">ONS</hi>
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= (<hi rend="italic">R</hi>
)‐salicylaldehyde thiosemicarbazonate(1−) R = 5,6‐C<hi rend="subscript">4</hi>
H<hi rend="subscript">4</hi>
(<hi rend="bold">3a</hi>
) or 3‐OMe (<hi rend="bold">3b</hi>
); (<hi rend="italic">ONS</hi>
)′ = (<hi rend="italic">R</hi>
)‐salicylaldehyde[benzylmercaptothiocarbonylhydrazonate(2−)], R = H, (<hi rend="bold">4a/5a</hi>
) or 3‐OMe (<hi rend="bold">4b/5b</hi>
)} have been prepared and characterised by IR, EPR, <hi rend="superscript">1</hi>
H‐, and <hi rend="superscript">51</hi>
V‐NMR spectroscopy. In (<hi rend="italic">S</hi>
)‐<hi rend="italic">s</hi>
BuOH, <hi rend="bold">4a</hi>
converts to [VO{(<hi rend="italic">S</hi>
)‐O<hi rend="italic">s</hi>
Bu}(<hi rend="italic">ONS</hi>
)′] (<hi rend="bold">5c</hi>
) and [VO(OH)(<hi rend="italic">ONS</hi>
)′] (or a condensation product thereof). Solutions of <hi rend="bold">5c</hi>
show three <hi rend="superscript">51</hi>
V NMR signals, two of which are due to two diastereomers. The EPR spectra of <hi rend="bold">3</hi>
and <hi rend="bold">4</hi>
in THF reveal the presence of octahedral species in solution. The crystal and molecular structures of complexes <hi rend="bold">3a·</hi>
OCMe<hi rend="subscript">2</hi>
, <hi rend="bold">5a</hi>
, and <hi rend="bold">5b</hi>
have been obtained, revealing basically a tetragonal pyramid, and coordination of the sulfur function in the thiocarbonyl (<hi rend="bold">3</hi>
) or enethiolate mode (<hi rend="bold">5</hi>
). The relevance of the compounds to bioinorganic aspects is addressed.</p>
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<titleGroup><title type="main" xml:lang="en">Vanadium(IV and V) Complexes Containing <i>SNO</i>
(Dithiocarbonylhydrazone; Thiosemicarbazone) Donor Sets</title>
<title type="short" xml:lang="en">Vanadium(IV and V) Complexes</title>
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<keywordGroup xml:lang="en" type="author"><keyword xml:id="kwd1">Vanadium</keyword>
<keyword xml:id="kwd2">Thiosemicarbazones</keyword>
<keyword xml:id="kwd3">Thiohydrazones</keyword>
<keyword xml:id="kwd4">Sulfur coordination</keyword>
<keyword xml:id="kwd5">Biomimetic compounds</keyword>
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<p>The VO<sup>2+</sup>
complexes [VOCl(<i>ONS</i>
)] (<b>3</b>
) and [VO(<i>ONS</i>
)′] (<b>4</b>
), and the VO<sup>3+</sup>
complexes [VO(OEt)(<i>ONS</i>
)′] (<b>5</b>
) {<i>ONS</i>
= (<i>R</i>
)‐salicylaldehyde thiosemicarbazonate(1−) R = 5,6‐C<sub>4</sub>
H<sub>4</sub>
(<b>3a</b>
) or 3‐OMe (<b>3b</b>
); (<i>ONS</i>
)′ = (<i>R</i>
)‐salicylaldehyde[benzylmercaptothiocarbonylhydrazonate(2−)], R = H, (<b>4a/5a</b>
) or 3‐OMe (<b>4b/5b</b>
)} have been prepared and characterised by IR, EPR, <sup>1</sup>
H‐, and <sup>51</sup>
V‐NMR spectroscopy. In (<i>S</i>
)‐<i>s</i>
BuOH, <b>4a</b>
converts to [VO{(<i>S</i>
)‐O<i>s</i>
Bu}(<i>ONS</i>
)′] (<b>5c</b>
) and [VO(OH)(<i>ONS</i>
)′] (or a condensation product thereof). Solutions of <b>5c</b>
show three <sup>51</sup>
V NMR signals, two of which are due to two diastereomers. The EPR spectra of <b>3</b>
and <b>4</b>
in THF reveal the presence of octahedral species in solution. The crystal and molecular structures of complexes <b>3a·</b>
OCMe<sub>2</sub>
, <b>5a</b>
, and <b>5b</b>
have been obtained, revealing basically a tetragonal pyramid, and coordination of the sulfur function in the thiocarbonyl (<b>3</b>
) or enethiolate mode (<b>5</b>
). The relevance of the compounds to bioinorganic aspects is addressed.</p>
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</role>
</name>
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<typeOfResource>text</typeOfResource>
<genre type="article" displayLabel="article" authority="ISTEX" authorityURI="https://content-type.data.istex.fr" valueURI="https://content-type.data.istex.fr/ark:/67375/XTP-6N5SZHKN-D">article</genre>
<originInfo><publisher>WILEY‐VCH Verlag GmbH</publisher>
<place><placeTerm type="text">Weinheim</placeTerm>
</place>
<dateIssued encoding="w3cdtf">2001-04</dateIssued>
<dateCaptured encoding="w3cdtf">2000-09-13</dateCaptured>
<copyrightDate encoding="w3cdtf">2001</copyrightDate>
</originInfo>
<language><languageTerm type="code" authority="rfc3066">en</languageTerm>
<languageTerm type="code" authority="iso639-2b">eng</languageTerm>
</language>
<physicalDescription><extent unit="figures">3</extent>
<extent unit="tables">4</extent>
<extent unit="references">59</extent>
</physicalDescription>
<abstract lang="en">The VO2+ complexes [VOCl(ONS)] (3) and [VO(ONS)′] (4), and the VO3+ complexes [VO(OEt)(ONS)′] (5) {ONS = (R)‐salicylaldehyde thiosemicarbazonate(1−) R = 5,6‐C4H4 (3a) or 3‐OMe (3b); (ONS)′ = (R)‐salicylaldehyde[benzylmercaptothiocarbonylhydrazonate(2−)], R = H, (4a/5a) or 3‐OMe (4b/5b)} have been prepared and characterised by IR, EPR, 1H‐, and 51V‐NMR spectroscopy. In (S)‐sBuOH, 4a converts to [VO{(S)‐OsBu}(ONS)′] (5c) and [VO(OH)(ONS)′] (or a condensation product thereof). Solutions of 5c show three 51V NMR signals, two of which are due to two diastereomers. The EPR spectra of 3 and 4 in THF reveal the presence of octahedral species in solution. The crystal and molecular structures of complexes 3a·OCMe2, 5a, and 5b have been obtained, revealing basically a tetragonal pyramid, and coordination of the sulfur function in the thiocarbonyl (3) or enethiolate mode (5). The relevance of the compounds to bioinorganic aspects is addressed.</abstract>
<subject lang="en"><genre>keywords</genre>
<topic>Vanadium</topic>
<topic>Thiosemicarbazones</topic>
<topic>Thiohydrazones</topic>
<topic>Sulfur coordination</topic>
<topic>Biomimetic compounds</topic>
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<relatedItem type="host"><titleInfo><title>European Journal of Inorganic Chemistry</title>
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<titleInfo type="abbreviated"><title>Eur. J. Inorg. Chem.</title>
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<subject><genre>article-category</genre>
<topic>Full Paper</topic>
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<identifier type="ISSN">1434-1948</identifier>
<identifier type="eISSN">1099-0682</identifier>
<identifier type="DOI">10.1002/(ISSN)1099-0682c</identifier>
<identifier type="PublisherID">EJIC</identifier>
<part><date>2001</date>
<detail type="volume"><caption>vol.</caption>
<number>2001</number>
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<detail type="issue"><caption>no.</caption>
<number>4</number>
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<extent unit="pages"><start>935</start>
<end>942</end>
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<note type="citation/reference">M. Busch , M. Starke , J. Prakt. Chem. 1916 , 93 , 59 .</note>
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