Synthesis and Reactivity of Organometallic Complexes of Divalent Thulium with Cyclopentadienyl and Phospholyl Ligands
详细信息 查看全文
- 作者：Florian Jaroschik ; Franç ; ois Nief ; Xavier-Fré ; dé ; ric Le Goff ; Louis Ricard
- 刊名：Organometallics
- 出版年：2007
- 出版时间：July 2, 2007
- 年：2007
- 卷：26
- 期：14
- 页码：3552 - 3558
- 全文大小：177K
- 年卷期：v.26,no.14(July 2, 2007)
- ISSN：1520-6041
文摘
Reaction of sodium 1,2,4-tris(trimethylsilyl)cyclopentadienide [Na(Cp' '')] with [TmI2(THF)3] affordedthe divalent thulium complex [(Cp' '')2Tm(THF)]. Its crystal structure is similar to that of the previouslydescribed [(Cpttt)2Tm(THF)] (Cpttt = 1,2,4-tris(tert-butyl)cyclopentadienyl). [(Cp' '')2TmI] was preparedby reaction of TmI3 with [K(Cp' '')] and could be reduced by KC8 into a new unsolvated, homolepticcomplex, [(Cp' '')2Tm], which was characterized by NMR. [(Cp' '')2Tm] gave [(Cp' '')2Tm(THF)] byinteraction with THF. A convenient alternative pathway to [(Cpttt)2Tm] by reduction of [(Cpttt)2Tm(BH4)] with KC8 was found: [(Cpttt)2Tm(BH4)] derives from [Tm(BH4)3(THF)3], which can be preparedfrom the less expensive TmCl3. On the other hand, the dimer [{(Cptt)2TmI}2] (Cptt = 1,3-bis(tert-butyl)cyclopentadienyl), obtained by reaction of TmI3 with [Na(Cptt)], gave only intractable results by reactionwith KC8. The previously described TmII complex [(Dtp)2Tm] (Dtp = 2,5-di-tert-butyl-3,4-dimethylphospholyl) and the new, homoleptic, structurally characterized TmII dimer [{(Htp)2Tm}2] (Htp = 2,5-di-tert-butylphospholyl) were prepared by KC8 reduction of [(Dtp)2TmI] and [{(Htp)2TmI}2], respectively. Reaction of [(Cpttt)2Tm] with pyridine resulted in an immediate reduction of pyridine into 1,1'-bis(1,4-dihydropyridylamide) and the formation of the structurally characterized [{(Cpttt)2Tm}2{
-(NC5H5-C5H5N)}], while the reaction of [(Dtp)2Tm] with pyridine gave no isolable complexes. An NMRstudy suggests that initially a simple TmII adduct such as [(Dtp)2Tm(pyridine)] is formed in this reaction.
-(NC5H5-C5H5N)}], while the reaction of [(Dtp)2Tm] with pyridine gave no isolable complexes. An NMRstudy suggests that initially a simple TmII adduct such as [(Dtp)2Tm(pyridine)] is formed in this reaction.