Structure and Reactivity of Homoleptic Samarium(II) and Thulium(II) Phospholyl Complexes
Identifieur interne : 002068 ( Istex/Corpus ); précédent : 002067; suivant : 002069Structure and Reactivity of Homoleptic Samarium(II) and Thulium(II) Phospholyl Complexes
Auteurs : Daniela Turcitu ; François Nief ; Louis RicardSource :
- Chemistry – A European Journal [ 0947-6539 ] ; 2003-10-17.
English descriptors
- KwdEn :
- Azobenzene, Azobenzene complexes, Bochkarev, Characterised, Chem, Crystal structure, Diethyl, Diethyl ether, Elemental analysis calcd, Ether, Full paper, General method, Gmbh, Homoleptic, Homoleptic complexes, Homoleptic smii, Kgaa, Ligand, Meff, Mmol, Nief, Organometallics, Pentane, Pentane solutions, Phospholyl, Phosphorus, Reaction mixture, Room temperature, Smii, Solid state, Thulium, Tmi2, Tmii, Tmii phospholyl complexes, Toluene, Toluene solutions, Triphenylphosphane sulfide, Verlag, Verlag gmbh, Weinheim, Weinheim chem, Ziller.
- Teeft :
- Azobenzene, Azobenzene complexes, Bochkarev, Characterised, Chem, Crystal structure, Diethyl, Diethyl ether, Elemental analysis calcd, Ether, Full paper, General method, Gmbh, Homoleptic, Homoleptic complexes, Homoleptic smii, Kgaa, Ligand, Meff, Mmol, Nief, Organometallics, Pentane, Pentane solutions, Phospholyl, Phosphorus, Reaction mixture, Room temperature, Smii, Solid state, Thulium, Tmi2, Tmii, Tmii phospholyl complexes, Toluene, Toluene solutions, Triphenylphosphane sulfide, Verlag, Verlag gmbh, Weinheim, Weinheim chem, Ziller.
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 SmI2 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 TmI2 in diethyl ether afforded [Tm(dsp)2(Et2O)], which could not be desolvated without decomposition. In contrast, the coordinated ether group of the solvate [Tm(dtp)2(Et2O)], obtained from 9 and TmI2, 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 TmII 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(N2Ph2)] (13), [Sm(dsp)2(N2Ph2)], (14) and [Sm(dtp)2(N2Ph2)] (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(μ‐S)] (16), which was characterised by X‐ray crystallography, whereas samarium(II) complexes 6 and 7 did not noticeably react with Ph3PS over 24 h under the same conditions.
Url:
DOI: 10.1002/chem.200305107
Links to Exploration step
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<front><div type="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 SmI2 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 TmI2 in diethyl ether afforded [Tm(dsp)2(Et2O)], which could not be desolvated without decomposition. In contrast, the coordinated ether group of the solvate [Tm(dtp)2(Et2O)], obtained from 9 and TmI2, 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 TmII 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(N2Ph2)] (13), [Sm(dsp)2(N2Ph2)], (14) and [Sm(dtp)2(N2Ph2)] (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(μ‐S)] (16), which was characterised by X‐ray crystallography, whereas samarium(II) complexes 6 and 7 did not noticeably react with Ph3PS over 24 h under the same conditions.</div>
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<profileDesc><abstract xml:lang="en" style="main"><head>Abstract</head>
<p>Potassium 2,5‐di‐<hi rend="italic">tert</hi>
‐butyl‐3,4‐dimethylphospholide K(dtp) (<hi rend="bold">9</hi>
) 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) (<hi rend="bold">8</hi>
) with SmI<hi rend="subscript">2</hi>
in diethyl ether afforded the homoleptic samarium(<hi rend="smallCaps">II</hi>
) complexes <hi rend="bold">7</hi>
and <hi rend="bold">6</hi>
, respectively, whose solid‐state structures, [{Sm(dtp)<hi rend="subscript">2</hi>
}<hi rend="subscript">2</hi>
] (<hi rend="bold">7 a</hi>
) and [{Sm(dsp)<hi rend="subscript">2</hi>
}<hi rend="subscript">2</hi>
] (<hi rend="bold">6 a</hi>
), are dimeric owing to coordination of the phosphorus lone pairs to samarium, as shown by X‐ray crystallography. Reaction of <hi rend="bold">8</hi>
with TmI<hi rend="subscript">2</hi>
in diethyl ether afforded [Tm(dsp)<hi rend="subscript">2</hi>
(Et<hi rend="subscript">2</hi>
O)], which could not be desolvated without decomposition. In contrast, the coordinated ether group of the solvate [Tm(dtp)<hi rend="subscript">2</hi>
(Et<hi rend="subscript">2</hi>
O)], obtained from <hi rend="bold">9</hi>
and TmI<hi rend="subscript">2</hi>
, could easily be removed by evaporation of the solvent and extraction with pentane at room temperature, and the monomer [Tm(dtp)<hi rend="subscript">2</hi>
] (<hi rend="bold">5</hi>
) could be isolated and was characterised by X‐ray crystallography. Presumably, steric crowding in <hi rend="bold">5</hi>
is too high for dimerisation to occur. Compound <hi rend="bold">5</hi>
, the first Tm<hi rend="superscript">II</hi>
homoleptic sandwich complex, is remarkably stable at room temperature in solution and did not noticeably react with nitrogen, in sharp contrast with other thulium(<hi rend="smallCaps">II</hi>
) species. As expected, <hi rend="bold">5, 6</hi>
and <hi rend="bold">7</hi>
all reacted with azobenzene to give the trivalent complexes [Tm(dtp)<hi rend="subscript">2</hi>
(N<hi rend="subscript">2</hi>
Ph<hi rend="subscript">2</hi>
)] (<hi rend="bold">13</hi>
), [Sm(dsp)<hi rend="subscript">2</hi>
(N<hi rend="subscript">2</hi>
Ph<hi rend="subscript">2</hi>
)], (<hi rend="bold">14</hi>
) and [Sm(dtp)<hi rend="subscript">2</hi>
(N<hi rend="subscript">2</hi>
Ph<hi rend="subscript">2</hi>
)] (<hi rend="bold">15</hi>
), respectively; <hi rend="bold">13</hi>
and <hi rend="bold">14</hi>
were characterised by X‐ray crystallography. Complex <hi rend="bold">5</hi>
immediately reacted with triphenylphosphane sulfide at room temperature to give [{Tm(dtp)<hi rend="subscript">2</hi>
}<hi rend="subscript">2</hi>
(<hi rend="italic">μ</hi>
‐S)] (<hi rend="bold">16</hi>
), which was characterised by X‐ray crystallography, whereas samarium(<hi rend="smallCaps">II</hi>
) complexes <hi rend="bold">6</hi>
and <hi rend="bold">7</hi>
did not noticeably react with Ph<hi rend="subscript">3</hi>
PS over 24 h under the same conditions.</p>
</abstract>
<abstract xml:lang="ro" style="main"><p>Anionul fosfolil K(dtp) (<hi rend="bold">9</hi>
) a fost obtinut pe baza chimiei zirconiului din materii prime comerciale cu un randament total de 45 %. Reactia acestuia cat si cea a anionului K(dsp) (<hi rend="bold">8</hi>
), descris anterior, cu SmI<hi rend="subscript">2</hi>
in Et<hi rend="subscript">2</hi>
O au condus la izolarea a doi complecsi homoleptici dimeri ai Sm<hi rend="superscript">II</hi>
(raze X) prin coordinarea perechii libere a fosforului de Sm. Complexul solvatat [Tm(dtp)<hi rend="subscript">2</hi>
(Et<hi rend="subscript">2</hi>
O)], obtinut din (<hi rend="bold">9</hi>
) in aceleasi conditii, pierde usor solventul coordinat prin extractie cu hexan, rezultand un complex monomer [Tm(dtp)<hi rend="subscript">2</hi>
] (<hi rend="bold">5</hi>
) (raze X). Probabil ca acest compus nu se prezinta sub forma unui dimer din cauza impiedicarii sterice. (<hi rend="bold">5</hi>
), primul complex sandwich homoleptic al Tm<hi rend="superscript">II</hi>
, prezinta stabilitate termica in solutie si este inert fata de N<hi rend="subscript">2</hi>
, contrar altor specii ale Tm<hi rend="superscript">II</hi>
. Compusii homoleptici ai Sm si Tm divalenti reactioneaza cu azobenzenul, obtinandu‐se speciile trivalente corespunzatoare, [Tm(dtp)<hi rend="subscript">2</hi>
(N<hi rend="subscript">2</hi>
Ph<hi rend="subscript">2</hi>
)] (<hi rend="bold">13</hi>
) si [Sm(dsp)<hi rend="subscript">2</hi>
(N<hi rend="subscript">2</hi>
Ph<hi rend="subscript">2</hi>
)] (<hi rend="bold">14</hi>
) (raze X). Compusul (<hi rend="bold">5</hi>
) reactioneaza instantaneu cu Ph<hi rend="subscript">3</hi>
P=S, la temperatura camerei, formand [Tm(dtp)<hi rend="subscript">2</hi>
(<hi rend="italic">μ</hi>
‐S)] (<hi rend="bold">16</hi>
), a carui structura a fost determinata, in timp ce complecsii Sm<hi rend="superscript">II</hi>
nu au dat nici un rezultat dupa 24 h in aceleasi conditii.</p>
</abstract>
<abstract xml:lang="en" style="graphical"><p><hi rend="bold">The first stable homoleptic Tm</hi>
<hi rend="superscript"><hi rend="bold">II</hi>
</hi>
<hi rend="bold">complex</hi>
(see picture) was isolated by using a bulky phospholyl ligand. This compound and analogous samarium(<hi rend="smallCaps">II</hi>
) phospholyl complexes display remarkably low reactivity. Bulky phospholyl ligands thus are promising for the stabilisation of other metals in unusually low oxidation states.<figure type="box"><media mimeType="image" url="urn:x-wiley:09476539:media:CHEM200305107:content"></media>
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</p>
</abstract>
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<term xml:id="kwd3">P ligands</term>
<term xml:id="kwd4">samarium</term>
<term xml:id="kwd5">thulium</term>
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<titleGroup><title type="main" xml:lang="en">Chemistry – A European Journal</title>
<title type="short">Chemistry – A European Journal</title>
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<publicationMeta level="part" position="200"><doi origin="wiley" registered="yes">10.1002/chem.v9:20</doi>
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<titleGroup><title type="main" xml:lang="en">Structure and Reactivity of Homoleptic Samarium(<sc>II</sc>
) and Thulium(<sc>II</sc>
) Phospholyl Complexes</title>
</titleGroup>
<creators><creator xml:id="au1" creatorRole="author" affiliationRef="#afa"><personName><givenNames>Daniela</givenNames>
<familyName>Turcitu</familyName>
</personName>
</creator>
<creator xml:id="au2" creatorRole="author" affiliationRef="#afa"><personName><givenNames>François</givenNames>
<familyName>Nief</familyName>
<degrees>Dr.</degrees>
</personName>
<contactDetails><email>nief@poly.polytechnique.fr</email>
</contactDetails>
</creator>
<creator xml:id="au3" creatorRole="author" affiliationRef="#afa"><personName><givenNames>Louis</givenNames>
<familyName>Ricard</familyName>
<degrees>Dr.</degrees>
</personName>
</creator>
</creators>
<affiliationGroup><affiliation xml:id="afa" countryCode="FR" type="organization"><unparsedAffiliation>Laboratoire Hétéroéléments et Coordination, CNRS UMR 7653, DCPH, Ecole Polytechnique, 91128 Palaiseau, France, Fax: (+33) 1‐69333990</unparsedAffiliation>
</affiliation>
</affiliationGroup>
<keywordGroup xml:lang="en" type="author"><keyword xml:id="kwd1">low‐valent compounds</keyword>
<keyword xml:id="kwd2">metallocenes</keyword>
<keyword xml:id="kwd3">P ligands</keyword>
<keyword xml:id="kwd4">samarium</keyword>
<keyword xml:id="kwd5">thulium</keyword>
</keywordGroup>
<abstractGroup><abstract type="main" xml:lang="en"><title type="main">Abstract</title>
<p>Potassium 2,5‐di‐<i>tert</i>
‐butyl‐3,4‐dimethylphospholide K(dtp) (<b>9</b>
) 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) (<b>8</b>
) with SmI<sub>2</sub>
in diethyl ether afforded the homoleptic samarium(<sc>II</sc>
) complexes <b>7</b>
and <b>6</b>
, respectively, whose solid‐state structures, [{Sm(dtp)<sub>2</sub>
}<sub>2</sub>
] (<b>7 a</b>
) and [{Sm(dsp)<sub>2</sub>
}<sub>2</sub>
] (<b>6 a</b>
), are dimeric owing to coordination of the phosphorus lone pairs to samarium, as shown by X‐ray crystallography. Reaction of <b>8</b>
with TmI<sub>2</sub>
in diethyl ether afforded [Tm(dsp)<sub>2</sub>
(Et<sub>2</sub>
O)], which could not be desolvated without decomposition. In contrast, the coordinated ether group of the solvate [Tm(dtp)<sub>2</sub>
(Et<sub>2</sub>
O)], obtained from <b>9</b>
and TmI<sub>2</sub>
, could easily be removed by evaporation of the solvent and extraction with pentane at room temperature, and the monomer [Tm(dtp)<sub>2</sub>
] (<b>5</b>
) could be isolated and was characterised by X‐ray crystallography. Presumably, steric crowding in <b>5</b>
is too high for dimerisation to occur. Compound <b>5</b>
, the first Tm<sup>II</sup>
homoleptic sandwich complex, is remarkably stable at room temperature in solution and did not noticeably react with nitrogen, in sharp contrast with other thulium(<sc>II</sc>
) species. As expected, <b>5, 6</b>
and <b>7</b>
all reacted with azobenzene to give the trivalent complexes [Tm(dtp)<sub>2</sub>
(N<sub>2</sub>
Ph<sub>2</sub>
)] (<b>13</b>
), [Sm(dsp)<sub>2</sub>
(N<sub>2</sub>
Ph<sub>2</sub>
)], (<b>14</b>
) and [Sm(dtp)<sub>2</sub>
(N<sub>2</sub>
Ph<sub>2</sub>
)] (<b>15</b>
), respectively; <b>13</b>
and <b>14</b>
were characterised by X‐ray crystallography. Complex <b>5</b>
immediately reacted with triphenylphosphane sulfide at room temperature to give [{Tm(dtp)<sub>2</sub>
}<sub>2</sub>
(<i>μ</i>
‐S)] (<b>16</b>
), which was characterised by X‐ray crystallography, whereas samarium(<sc>II</sc>
) complexes <b>6</b>
and <b>7</b>
did not noticeably react with Ph<sub>3</sub>
PS over 24 h under the same conditions.</p>
</abstract>
<abstract type="main" xml:lang="ro"><p>Anionul fosfolil K(dtp) (<b>9</b>
) a fost obtinut pe baza chimiei zirconiului din materii prime comerciale cu un randament total de 45 %. Reactia acestuia cat si cea a anionului K(dsp) (<b>8</b>
), descris anterior, cu SmI<sub>2</sub>
in Et<sub>2</sub>
O au condus la izolarea a doi complecsi homoleptici dimeri ai Sm<sup>II</sup>
(raze X) prin coordinarea perechii libere a fosforului de Sm. Complexul solvatat [Tm(dtp)<sub>2</sub>
(Et<sub>2</sub>
O)], obtinut din (<b>9</b>
) in aceleasi conditii, pierde usor solventul coordinat prin extractie cu hexan, rezultand un complex monomer [Tm(dtp)<sub>2</sub>
] (<b>5</b>
) (raze X). Probabil ca acest compus nu se prezinta sub forma unui dimer din cauza impiedicarii sterice. (<b>5</b>
), primul complex sandwich homoleptic al Tm<sup>II</sup>
, prezinta stabilitate termica in solutie si este inert fata de N<sub>2</sub>
, contrar altor specii ale Tm<sup>II</sup>
. Compusii homoleptici ai Sm si Tm divalenti reactioneaza cu azobenzenul, obtinandu‐se speciile trivalente corespunzatoare, [Tm(dtp)<sub>2</sub>
(N<sub>2</sub>
Ph<sub>2</sub>
)] (<b>13</b>
) si [Sm(dsp)<sub>2</sub>
(N<sub>2</sub>
Ph<sub>2</sub>
)] (<b>14</b>
) (raze X). Compusul (<b>5</b>
) reactioneaza instantaneu cu Ph<sub>3</sub>
P=S, la temperatura camerei, formand [Tm(dtp)<sub>2</sub>
(<i>μ</i>
‐S)] (<b>16</b>
), a carui structura a fost determinata, in timp ce complecsii Sm<sup>II</sup>
nu au dat nici un rezultat dupa 24 h in aceleasi conditii.</p>
</abstract>
<abstract type="graphical" xml:lang="en"><p><b>The first stable homoleptic Tm</b>
<sup><b>II</b>
</sup>
<b>complex</b>
(see picture) was isolated by using a bulky phospholyl ligand. This compound and analogous samarium(<sc>II</sc>
) phospholyl complexes display remarkably low reactivity. Bulky phospholyl ligands thus are promising for the stabilisation of other metals in unusually low oxidation states.<blockFixed type="graphic"><mediaResourceGroup><mediaResource alt="image" eRights="yes" copyright="WILEY-VCH" href="urn:x-wiley:09476539:media:CHEM200305107:content"></mediaResource>
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<name type="personal"><namePart type="given">Daniela</namePart>
<namePart type="family">Turcitu</namePart>
<affiliation>Laboratoire Hétéroéléments et Coordination, CNRS UMR 7653, DCPH, Ecole Polytechnique, 91128 Palaiseau, France, Fax: (+33) 1‐69333990</affiliation>
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<name type="personal"><namePart type="given">François</namePart>
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<affiliation>Laboratoire Hétéroéléments et Coordination, CNRS UMR 7653, DCPH, Ecole Polytechnique, 91128 Palaiseau, France, Fax: (+33) 1‐69333990</affiliation>
<affiliation>E-mail: nief@poly.polytechnique.fr</affiliation>
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</role>
</name>
<name type="personal"><namePart type="given">Louis</namePart>
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<namePart type="termsOfAddress">Dr.</namePart>
<affiliation>Laboratoire Hétéroéléments et Coordination, CNRS UMR 7653, DCPH, Ecole Polytechnique, 91128 Palaiseau, France, Fax: (+33) 1‐69333990</affiliation>
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<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 SmI2 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 TmI2 in diethyl ether afforded [Tm(dsp)2(Et2O)], which could not be desolvated without decomposition. In contrast, the coordinated ether group of the solvate [Tm(dtp)2(Et2O)], obtained from 9 and TmI2, 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 TmII 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(N2Ph2)] (13), [Sm(dsp)2(N2Ph2)], (14) and [Sm(dtp)2(N2Ph2)] (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(μ‐S)] (16), which was characterised by X‐ray crystallography, whereas samarium(II) complexes 6 and 7 did not noticeably react with Ph3PS over 24 h under the same conditions.</abstract>
<abstract>Anionul fosfolil K(dtp) (9) a fost obtinut pe baza chimiei zirconiului din materii prime comerciale cu un randament total de 45 %. Reactia acestuia cat si cea a anionului K(dsp) (8), descris anterior, cu SmI2 in Et2O au condus la izolarea a doi complecsi homoleptici dimeri ai SmII (raze X) prin coordinarea perechii libere a fosforului de Sm. Complexul solvatat [Tm(dtp)2(Et2O)], obtinut din (9) in aceleasi conditii, pierde usor solventul coordinat prin extractie cu hexan, rezultand un complex monomer [Tm(dtp)2] (5) (raze X). Probabil ca acest compus nu se prezinta sub forma unui dimer din cauza impiedicarii sterice. (5), primul complex sandwich homoleptic al TmII, prezinta stabilitate termica in solutie si este inert fata de N2, contrar altor specii ale TmII. Compusii homoleptici ai Sm si Tm divalenti reactioneaza cu azobenzenul, obtinandu‐se speciile trivalente corespunzatoare, [Tm(dtp)2(N2Ph2)] (13) si [Sm(dsp)2(N2Ph2)] (14) (raze X). Compusul (5) reactioneaza instantaneu cu Ph3P=S, la temperatura camerei, formand [Tm(dtp)2(μ‐S)] (16), a carui structura a fost determinata, in timp ce complecsii SmII nu au dat nici un rezultat dupa 24 h in aceleasi conditii.</abstract>
<abstract>The first stable homoleptic TmII complex (see picture) was isolated by using a bulky phospholyl ligand. This compound and analogous samarium(II) phospholyl complexes display remarkably low reactivity. Bulky phospholyl ligands thus are promising for the stabilisation of other metals in unusually low oxidation states.</abstract>
<subject lang="en"><genre>keywords</genre>
<topic>low‐valent compounds</topic>
<topic>metallocenes</topic>
<topic>P ligands</topic>
<topic>samarium</topic>
<topic>thulium</topic>
</subject>
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<detail type="volume"><caption>vol.</caption>
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