12‐Vertex Zwitterionic Bis‐phosphonium‐nido‐carborates through Ring‐Opening Reactions of 1,2‐Diphosphetanes,Chemistry - A European Journal

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12‐Vertex Zwitterionic Bis‐phosphonium‐nido‐carborates through Ring‐Opening Reactions of 1,2‐Diphosphetanes
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2018-03-26 , DOI: 10.1002/chem.201800172
Jan Schulz ₁ , Anika Kreienbrink ₁ , Peter Coburger ₁ , Benedikt Schwarze ₁ , Toni Grell ₁ , Peter Lönnecke ₁ , Evamarie Hey-Hawkins ₁

Affiliation

Carborane‐substituted 1,2‐diphosphetanes (Ia,b) react with elemental lithium in THF with cleavage of the P−P bond to give a deep red solution from which, in the case of Ia, red crystals of a lithiated intermediate, [{1‐Li(THF)PtBu‐6‐PtBu‐4,1,6‐closo‐Li(THF)C₂B₁₀H₁₀}{Li(THF)₃}]₂⋅2 THF (2 a), are obtained. The compound is dimeric, C₂‐symmetric and contains six lithium and four phosphorus atoms. Two lithium atoms cap the six‐membered C₂B₄ faces, resulting in two 13‐vertex closo‐clusters (according to Wade's rules) with docosahedral geometry. The addition of methyl iodide resulted in the formation of zwitterionic bis‐phosphonium‐nido‐carborates 7,10‐bis(tert‐butyldimethylphosphonium)dodecahydro‐7,10‐dicarba‐nido‐dodecaborate(2−) (1 a) and 7,10‐bis(N,N‐diisopropylaminodimethylphosphonium)dodecahydro‐7,10‐dicarba‐nido‐dodecaborate(2−) (1 b) in moderate to good yields. Compounds 1 a and 1 b exhibit short C_cluster−P bonds and large C_cluster⋅⋅⋅C_cluster distances in the solid state. Further insight into the ring opening and reduction potential of the alkyl halide was obtained from methylation reactions of different 1,2‐bis‐phosphinocarboranes. The reaction of rac‐/meso‐1,2‐bis(tert‐butylmethylphosphino)‐1,2‐dicarba‐closo‐dodecaborane(12) (3 a) with two equivalents of methyl iodide also resulted in the formation of 1 a (as shown by NMR spectroscopy), whereas the reaction of 1,2‐bis(diphenylphosphino)‐1,2‐dicarba‐closo‐dodecaborane(12) with methyl triflate afforded the phosphonium salt 1‐methyl‐diphenylphosphonium‐2‐diphenylphosphino‐1,2‐dicarba‐closo‐dodecaborane(12) triflate (4) without reduction of the cluster.

中文翻译：

通过1,2-二膦环烷的开环反应生成12顶点两性离子双Bi-氮碳酸盐

碳硼烷取代的1,2-二膦酸酯（Ia，b）与元素锂在THF中反应，裂解P-P键，得到深红色溶液，在Ia的情况下，由深红色溶液从锂化的中间体中形成红色晶体，[ {1-锂（THF）p吨卜-6-P吨卜4,1,6-闭合碳-Li（THF）C ₂乙₁₀ ħ ₁₀ } {锂（THF）₃ }] ₂⋅ 2 THF（2 a），得到。该化合物为二聚体，C ₂对称，包含六个锂和四个磷原子。两个锂原子覆盖六元碳₂ B ₄面，形成两个具有二十面体几何形状的13顶点closo簇（根据Wade的规则）。甲基碘的加入导致形成两性离子双膦酸氮鎓碳酸盐7,10-双（叔丁基二甲基phosph）十二烷基氢-7,10-二氨基甲酰十二碳酸盐（2-）（1 a）和7， 10-双（N，N-二异丙基氨基二甲基phosph）十二氢化-7,10-二氨基甲酸酯-十二硼酸酯（2-）（1 b），产率中等至良好。化合物1a和1b表现出短的C_簇-P键和大的C_簇固态的⋅⋅⋅C_簇距离。从不同的1,2-双膦基碳硼烷的甲基化反应中，可以进一步了解卤代烷的开环和还原潜力。的反应外消旋- /内消旋-1,2-双（叔-butylmethylphosphino）-1,2- dicarba-闭合碳-dodecaborane（12）（3）与甲基的两个当量碘化物也导致形成1（如通过NMR光谱示出），而1,2-双（二苯基膦基）-1,2- dicarba-反应闭合碳-dodecaborane（12）与三氟甲磺酸甲酯，得到鏻盐1-甲基diphenylphosphonium -2-二苯基膦基-1- ，2- dicarba-闭合碳‐dodecaborane（12）三氟甲磺酸酯（4），而不会减少簇。

更新日期：2018-03-26

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