Synthesis and reactivity of organometallic complexes of divalent thulium with cyclopentadienyl and phospholyl ligands
Synthesis and reactivity of organometallic complexes of divalent thulium with cyclopentadienyl and phospholyl ligands
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DOI：
10.1021/om700316a
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发表时间：
2007-07-02
期刊：
影响因子：
2.8
通讯作者：
Ricard, Louis
中科院分区：
文献类型：
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作者：
Jaroschik, Florian;Nief, Francois;Ricard, Louis
1，2，4-三（三甲基硅基）环戊二烯钠[Na（Cp“”）]与[TmI 2（THF）（3）]反应，得到二价铥配合物[（Cp“”）（2）Tm（THF）]。其晶体结构类似于先前描述的[（Cp-ttt）（2）Tm（THF）]（Cp-ttt = 1，2，4-三（叔丁基）Tm）。[(Cp TmI 3与[K（Cp“”）]反应制得[（Cp“”）（2）TmI]，并经KCl 8还原得到一种新的非溶剂化均配型配合物[（Cp "“）（2）Tm]，其结构经NMR表征。[(Cp（Cp“”）（2）Tm]与THF作用得到[（Cp“”）（2）Tm（THF）]。发现了通过用KCl 8还原[（Cp-ttt）（2）Tm（BH 4）]得到[（Cp-ttt）（2）Tm]的方便的替代途径：[（Cp-ttt）（2）Tm（BH 4）]衍生自[Tm（BH 4）（3）（THF）（3）]，其可以从较便宜的TmCl 3制备。另一方面，通过TmI 3与[Na（Cp-tt）]反应得到的二聚体[{（Cp-tt）（2）TmI}（2）]（Cp-tt = 1，3-双（叔丁基）碘），通过与KCl 8反应只能得到难以处理的结果。先前描述的Tm-II复合物[（Dtp）（2）Tm]（Dtp = 2，5-二叔丁基-3，4-二甲基磷酰基）和新的均配的、结构表征的Tm-II二聚体[{（Htp）（2）Tm}（2）]（Htp = 2，5-二叔丁基磷酰基）分别通过[（Dtp）（2）TmI]和[{（Htp）（2）TmI}（2）]的KC 8还原制备。[（Cp-ttt）（2）Tm]与吡啶反应后，吡啶立即被还原成1，1 ′-双（1，4-二氢吡啶酰胺），并形成结构表征的[{（Cp-ttt）（2）Tm}（2）{mu-（NC_5 H_5-C_5 H_5 N）}]，而[（Dtp）（2）Tm]与吡啶反应后，没有得到可分离的配合物。NMR研究表明，最初在该反应中形成简单的Tm-II加合物，例如[（Dtp）（2）Tm（吡啶）]。
Reaction of sodium 1,2,4-tris(trimethylsilyl)cyclopentadienide [Na(Cp' '')] with [TmI2(THF)(3)] afforded the divalent thulium complex [(Cp' '')(2)Tm(THF)]. Its crystal structure is similar to that of the previously described [(Cp-ttt)(2)Tm(THF)] (Cp-ttt = 1,2,4-tris(tert-butyl)cyclopentadienyl). [(Cp' '')(2)TmI] was prepared by reaction of TmI3 with [K(Cp' '')] and could be reduced by KC8 into a new unsolvated, homoleptic complex, [(Cp' '')(2)Tm], which was characterized by NMR. [(Cp' '')(2)Tm] gave [(Cp' '')(2)Tm(THF)] by interaction with THF. A convenient alternative pathway to [(Cp-ttt)(2)Tm] by reduction of [(Cp-ttt)(2)Tm(BH4)] with KC8 was found: [(Cp-ttt)(2)Tm(BH4)] derives from [Tm(BH4)(3)(THF)(3)], which can be prepared from the less expensive TmCl3. On the other hand, the dimer [{(Cp-tt)(2)TmI}(2)] (Cp-tt = 1,3-bis(tert-butyl)cyclopentadienyl), obtained by reaction of TmI3 with [Na(Cp-tt)], gave only intractable results by reaction with KC8. The previously described Tm-II complex [(Dtp)(2)Tm] (Dtp = 2,5-di-tert-butyl-3,4-dimethylphospholyl) and the new, homoleptic, structurally characterized Tm-II dimer [{(Htp)(2)Tm}(2)] (Htp = 2,5-di-tert-butylphospholyl) were prepared by KC8 reduction of [(Dtp)(2)TmI] and [{(Htp)(2)TmI}(2)], respectively. Reaction of [(Cp-ttt)(2)Tm] with pyridine resulted in an immediate reduction of pyridine into 1,1'-bis(1,4-dihydropyridylamide) and the formation of the structurally characterized [{(Cp-ttt)(2)Tm}(2){mu-(NC5H5-C5H5N)}], while the reaction of [(Dtp)(2)Tm] with pyridine gave no isolable complexes. An NMR study suggests that initially a simple Tm-II adduct such as [(Dtp)(2)Tm(pyridine)] is formed in this reaction.