Structure and reactivity of homoleptic samarium(II) and thulium(II) phospholyl complexes.
Identifieur interne : 000657 ( PubMed/Checkpoint ); précédent : 000656; suivant : 000658Structure and reactivity of homoleptic samarium(II) and thulium(II) phospholyl complexes.
Auteurs : Daniela Turcitu [France] ; François Nief ; Louis RicardSource :
- Chemistry (Weinheim an der Bergstrasse, Germany) [ 0947-6539 ] ; 2003.
Abstract
Potassium 2,5-di-tert-butyl-3,4-dimethylphospholide K(dtp) (9) was synthesised in 45 % yield from commercially available starting materials by using zirconacyclopentadiene chemistry. Reaction of the K salt of this bulky anion and of the previously described potassium 2,5-bis(trimethylsilyl)-3,4-dimethylphospholide K(dsp) (8) with SmI(2) in diethyl ether afforded the homoleptic samarium(II) complexes 7 and 6, respectively, whose solid-state structures, [[Sm(dtp)(2)](2)] (7 a) and [[Sm(dsp)(2)](2)] (6 a), are dimeric owing to coordination of the phosphorus lone pairs to samarium, as shown by X-ray crystallography. Reaction of 8 with TmI(2) in diethyl ether afforded [Tm(dsp)(2)(Et(2)O)], which could not be desolvated without decomposition. In contrast, the coordinated ether group of the solvate [Tm(dtp)(2)(Et(2)O)], obtained from 9 and TmI(2), could easily be removed by evaporation of the solvent and extraction with pentane at room temperature, and the monomer [Tm(dtp)(2)] (5) could be isolated and was characterised by X-ray crystallography. Presumably, steric crowding in 5 is too high for dimerisation to occur. Compound 5, the first Tm(II) homoleptic sandwich complex, is remarkably stable at room temperature in solution and did not noticeably react with nitrogen, in sharp contrast with other thulium(II) species. As expected, 5, 6 and 7 all reacted with azobenzene to give the trivalent complexes [Tm(dtp)(2)(N(2)Ph(2))] (13), [Sm(dsp)(2)(N(2)Ph(2))], (14) and [Sm(dtp)(2)(N(2)Ph(2))] (15), respectively; 13 and 14 were characterised by X-ray crystallography. Complex 5 immediately reacted with triphenylphosphane sulfide at room temperature to give [[Tm(dtp)(2)](2)(mu-S)] (16), which was characterised by X-ray crystallography, whereas samarium(II) complexes 6 and 7 did not noticeably react with Ph(3)PS over 24 h under the same conditions.
DOI: 10.1002/chem.200305107
PubMed: 14562310
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Reaction of the K salt of this bulky anion and of the previously described potassium 2,5-bis(trimethylsilyl)-3,4-dimethylphospholide K(dsp) (8) with SmI(2) in diethyl ether afforded the homoleptic samarium(II) complexes 7 and 6, respectively, whose solid-state structures, [[Sm(dtp)(2)](2)] (7 a) and [[Sm(dsp)(2)](2)] (6 a), are dimeric owing to coordination of the phosphorus lone pairs to samarium, as shown by X-ray crystallography. Reaction of 8 with TmI(2) in diethyl ether afforded [Tm(dsp)(2)(Et(2)O)], which could not be desolvated without decomposition. In contrast, the coordinated ether group of the solvate [Tm(dtp)(2)(Et(2)O)], obtained from 9 and TmI(2), could easily be removed by evaporation of the solvent and extraction with pentane at room temperature, and the monomer [Tm(dtp)(2)] (5) could be isolated and was characterised by X-ray crystallography. Presumably, steric crowding in 5 is too high for dimerisation to occur. Compound 5, the first Tm(II) homoleptic sandwich complex, is remarkably stable at room temperature in solution and did not noticeably react with nitrogen, in sharp contrast with other thulium(II) species. As expected, 5, 6 and 7 all reacted with azobenzene to give the trivalent complexes [Tm(dtp)(2)(N(2)Ph(2))] (13), [Sm(dsp)(2)(N(2)Ph(2))], (14) and [Sm(dtp)(2)(N(2)Ph(2))] (15), respectively; 13 and 14 were characterised by X-ray crystallography. Complex 5 immediately reacted with triphenylphosphane sulfide at room temperature to give [[Tm(dtp)(2)](2)(mu-S)] (16), which was characterised by X-ray crystallography, whereas samarium(II) complexes 6 and 7 did not noticeably react with Ph(3)PS over 24 h under the same conditions.</div></front></TEI><pubmed><MedlineCitation Owner="NLM" Status="PubMed-not-MEDLINE"><PMID Version="1">14562310</PMID><DateCreated><Year>2003</Year><Month>10</Month><Day>16</Day></DateCreated><DateCompleted><Year>2004</Year><Month>05</Month><Day>11</Day></DateCompleted><DateRevised><Year>2009</Year><Month>08</Month><Day>04</Day></DateRevised><Article PubModel="Print"><Journal><ISSN IssnType="Print">0947-6539</ISSN><JournalIssue CitedMedium="Print"><Volume>9</Volume><Issue>20</Issue><PubDate><Year>2003</Year><Month>Oct</Month><Day>17</Day></PubDate></JournalIssue><Title>Chemistry (Weinheim an der Bergstrasse, Germany)</Title><ISOAbbreviation>Chemistry</ISOAbbreviation></Journal><ArticleTitle>Structure and reactivity of homoleptic samarium(II) and thulium(II) phospholyl complexes.</ArticleTitle><Pagination><MedlinePgn>4916-23</MedlinePgn></Pagination><Abstract><AbstractText>Potassium 2,5-di-tert-butyl-3,4-dimethylphospholide K(dtp) (9) was synthesised in 45 % yield from commercially available starting materials by using zirconacyclopentadiene chemistry. Reaction of the K salt of this bulky anion and of the previously described potassium 2,5-bis(trimethylsilyl)-3,4-dimethylphospholide K(dsp) (8) with SmI(2) in diethyl ether afforded the homoleptic samarium(II) complexes 7 and 6, respectively, whose solid-state structures, [[Sm(dtp)(2)](2)] (7 a) and [[Sm(dsp)(2)](2)] (6 a), are dimeric owing to coordination of the phosphorus lone pairs to samarium, as shown by X-ray crystallography. Reaction of 8 with TmI(2) in diethyl ether afforded [Tm(dsp)(2)(Et(2)O)], which could not be desolvated without decomposition. In contrast, the coordinated ether group of the solvate [Tm(dtp)(2)(Et(2)O)], obtained from 9 and TmI(2), could easily be removed by evaporation of the solvent and extraction with pentane at room temperature, and the monomer [Tm(dtp)(2)] (5) could be isolated and was characterised by X-ray crystallography. Presumably, steric crowding in 5 is too high for dimerisation to occur. Compound 5, the first Tm(II) homoleptic sandwich complex, is remarkably stable at room temperature in solution and did not noticeably react with nitrogen, in sharp contrast with other thulium(II) species. As expected, 5, 6 and 7 all reacted with azobenzene to give the trivalent complexes [Tm(dtp)(2)(N(2)Ph(2))] (13), [Sm(dsp)(2)(N(2)Ph(2))], (14) and [Sm(dtp)(2)(N(2)Ph(2))] (15), respectively; 13 and 14 were characterised by X-ray crystallography. Complex 5 immediately reacted with triphenylphosphane sulfide at room temperature to give [[Tm(dtp)(2)](2)(mu-S)] (16), which was characterised by X-ray crystallography, whereas samarium(II) complexes 6 and 7 did not noticeably react with Ph(3)PS over 24 h under the same conditions.</AbstractText></Abstract><AuthorList CompleteYN="Y"><Author ValidYN="Y"><LastName>Turcitu</LastName><ForeName>Daniela</ForeName><Initials>D</Initials><AffiliationInfo><Affiliation>Laboratoire Hétéroéléments et Coordination, CNRS UMR 7653, DCPH, Ecole Polytechnique, 91128 Palaiseau, France.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Nief</LastName><ForeName>François</ForeName><Initials>F</Initials></Author><Author ValidYN="Y"><LastName>Ricard</LastName><ForeName>Louis</ForeName><Initials>L</Initials></Author></AuthorList><Language>eng</Language><PublicationTypeList><PublicationType UI="D016428">Journal Article</PublicationType></PublicationTypeList></Article><MedlineJournalInfo><Country>Germany</Country><MedlineTA>Chemistry</MedlineTA><NlmUniqueID>9513783</NlmUniqueID><ISSNLinking>0947-6539</ISSNLinking></MedlineJournalInfo></MedlineCitation><PubmedData><History><PubMedPubDate PubStatus="pubmed"><Year>2003</Year><Month>10</Month><Day>17</Day><Hour>5</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="medline"><Year>2003</Year><Month>10</Month><Day>17</Day><Hour>5</Hour><Minute>1</Minute></PubMedPubDate><PubMedPubDate PubStatus="entrez"><Year>2003</Year><Month>10</Month><Day>17</Day><Hour>5</Hour><Minute>0</Minute></PubMedPubDate></History><PublicationStatus>ppublish</PublicationStatus><ArticleIdList><ArticleId IdType="pubmed">14562310</ArticleId><ArticleId IdType="doi">10.1002/chem.200305107</ArticleId></ArticleIdList></PubmedData></pubmed><affiliations><list><country><li>France</li></country><region><li>Île-de-France</li></region><settlement><li>Palaiseau</li></settlement></list><tree><noCountry><name sortKey="Nief, Francois" sort="Nief, Francois" uniqKey="Nief F" first="François" last="Nief">François Nief</name><name sortKey="Ricard, Louis" sort="Ricard, Louis" uniqKey="Ricard L" first="Louis" last="Ricard">Louis Ricard</name></noCountry><country name="France"><region name="Île-de-France"><name sortKey="Turcitu, Daniela" sort="Turcitu, Daniela" uniqKey="Turcitu D" first="Daniela" last="Turcitu">Daniela Turcitu</name></region></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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