Structure and Reactivity of Homoleptic Samarium(II) and Thulium(II) Phospholyl Complexes
Identifieur interne : 002068 ( Istex/Curation ); précédent : 002067; suivant : 002069Structure and Reactivity of Homoleptic Samarium(II) and Thulium(II) Phospholyl Complexes
Auteurs : Daniela Turcitu ; François Nief [France] ; Louis RicardSource :
- Chemistry – A European Journal [ 0947-6539 ] ; 2003-10-17.
Descripteurs français
- Wicri :
- topic : Phosphore.
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
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Daniela Turcitu<affiliation><mods:affiliation>Laboratoire Hétéroéléments et Coordination, CNRS UMR 7653, DCPH, Ecole Polytechnique, 91128 Palaiseau, France, Fax: (+33) 1‐69333990</mods:affiliation>
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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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