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Vanadium(IV and V) Complexes Containing SNO (Dithiocarbonylhydrazone; Thiosemicarbazone) Donor Sets

Identifieur interne : 001461 ( Istex/Corpus ); précédent : 001460; suivant : 001462

Vanadium(IV and V) Complexes Containing SNO (Dithiocarbonylhydrazone; Thiosemicarbazone) Donor Sets

Auteurs : Dongren Wang ; Martin Ebel ; Carola Schulzke ; Cerstin Grüning ; Saroj K. S. Hazari ; Dieter Rehder

Source :

RBID : ISTEX:122656417362142D58C0876219DC0EE36DEFD996

English descriptors

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

ISTEX:122656417362142D58C0876219DC0EE36DEFD996

Le document en format XML

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<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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<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>
)′] (
<hi rend="bold">4</hi>
), and the VO
<hi rend="superscript">3+</hi>
complexes [VO(OEt)(
<hi rend="italic">ONS</hi>
)′] (
<hi rend="bold">5</hi>
) {
<hi rend="italic">ONS</hi>
= (
<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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<i>SNO</i>
(Dithiocarbonylhydrazone; Thiosemicarbazone) Donor Sets</title>
<title type="short" xml:lang="en">Vanadium(IV and V) Complexes</title>
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<keyword xml:id="kwd4">Sulfur coordination</keyword>
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<title type="main">Abstract</title>
<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>
</abstract>
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<mods version="3.6">
<titleInfo lang="en">
<title>Vanadium(IV and V) Complexes Containing SNO (Dithiocarbonylhydrazone; Thiosemicarbazone) Donor Sets</title>
</titleInfo>
<titleInfo type="abbreviated" lang="en">
<title>Vanadium(IV and V) Complexes</title>
</titleInfo>
<titleInfo type="alternative" contentType="CDATA" lang="en">
<title>Vanadium(IV and V) Complexes Containing SNO (Dithiocarbonylhydrazone; Thiosemicarbazone) Donor Sets</title>
</titleInfo>
<name type="personal">
<namePart type="given">Dongren</namePart>
<namePart type="family">Wang</namePart>
<affiliation>Institut für Anorganische und Angewandte Chemie, Universität Hamburg, 20146 Hamburg, Germany</affiliation>
<role>
<roleTerm type="text">author</roleTerm>
</role>
</name>
<name type="personal">
<namePart type="given">Martin</namePart>
<namePart type="family">Ebel</namePart>
<affiliation>Institut für Anorganische und Angewandte Chemie, Universität Hamburg, 20146 Hamburg, Germany</affiliation>
<role>
<roleTerm type="text">author</roleTerm>
</role>
</name>
<name type="personal">
<namePart type="given">Carola</namePart>
<namePart type="family">Schulzke</namePart>
<affiliation>Institut für Anorganische und Angewandte Chemie, Universität Hamburg, 20146 Hamburg, Germany</affiliation>
<role>
<roleTerm type="text">author</roleTerm>
</role>
</name>
<name type="personal">
<namePart type="given">Cerstin</namePart>
<namePart type="family">Grüning</namePart>
<affiliation>Institut für Anorganische und Angewandte Chemie, Universität Hamburg, 20146 Hamburg, Germany</affiliation>
<role>
<roleTerm type="text">author</roleTerm>
</role>
</name>
<name type="personal">
<namePart type="given">Saroj K. S.</namePart>
<namePart type="family">Hazari</namePart>
<affiliation>Department of Chemistry, University of Chittagong, Chittagong, Bangladesh</affiliation>
<affiliation>E-mail: tapashi@ctgu.edu</affiliation>
<role>
<roleTerm type="text">author</roleTerm>
</role>
</name>
<name type="personal">
<namePart type="given">Dieter</namePart>
<namePart type="family">Rehder</namePart>
<affiliation>Institut für Anorganische und Angewandte Chemie, Universität Hamburg, 20146 Hamburg, Germany</affiliation>
<affiliation>E-mail: rehder@xray.chemie.uni‐hamburg.de</affiliation>
<role>
<roleTerm type="text">author</roleTerm>
</role>
</name>
<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>
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<physicalDescription>
<extent unit="figures">3</extent>
<extent unit="tables">4</extent>
<extent unit="references">59</extent>
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<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>
</subject>
<relatedItem type="host">
<titleInfo>
<title>European Journal of Inorganic Chemistry</title>
</titleInfo>
<titleInfo type="abbreviated">
<title>Eur. J. Inorg. Chem.</title>
</titleInfo>
<genre type="journal" authority="ISTEX" authorityURI="https://publication-type.data.istex.fr" valueURI="https://publication-type.data.istex.fr/ark:/67375/JMC-0GLKJH51-B">journal</genre>
<subject>
<genre>article-category</genre>
<topic>Full Paper</topic>
</subject>
<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>
</detail>
<detail type="issue">
<caption>no.</caption>
<number>4</number>
</detail>
<extent unit="pages">
<start>935</start>
<end>942</end>
<total>8</total>
</extent>
</part>
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