Rhodium-catalyzed dehydrocoupling of the sterically encumbered phosphine-borane adduct tBu2PH•BH3:: Synthesis of the linear dimers tBu2PH-BH2-tBu2P-BH3 and tBu2PH-BH2-tBu2P-BH2Cl
Rhodium-catalyzed dehydrocoupling of the sterically encumbered phosphine-borane adduct tBu2PH•BH3:: Synthesis of the linear dimers tBu2PH-BH2-tBu2P-BH3 and tBu2PH-BH2-tBu2P-BH2Cl
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DOI：
10.1021/ic0100626
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发表时间：
2001-08-13
影响因子：
4.6
通讯作者：
Manners, I
中科院分区：
文献类型：
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作者：
Dorn, H;Vejzovic, E;Manners, I
位阻膦-硼烷加合物 tBu(2)PH 的脱氢偶联。 BH3在140℃以上被铑配合物[Rh(1,5-cod)(2)][OTf]或Rh-6(CO)(16)催化生成四元链tBu(2)PH-BH2-tBu(2)P-BH3 (1)，其分离度为60%。产量和。通过多核核磁共振波谱、质谱和元素分析进行表征。 1在175-180℃的温度范围内热解导致部分分解并形成tBu(2)PH。 BH3。当tBu(2)PH脱氢偶联时。 BH3在[{Rh(mu -Cl)(1,5-cod)}2]或RhCl3水合物存在下进行，形成氯化化合物tBu(2)PH-BH2-tBu(2)P-BH2-Cl (2)，该化合物不能在没有1的情况下获得。 tBu(2)PH的分子结构。通过单晶 X 射线衍射研究测定了 BH3、tBu(2)PH-BH2-tBu(2)P-BH3 (1) 和 tBu(2)PH-BH2-tBu(2)P-BH2Cl (2) 以及 1。
The dehydrocoupling of the sterically hindered phosphine-borane adduct tBu(2)PH . BH3 above 140 degreesC is catalyzed by the rhodium complexes [Rh(1,5-cod)(2)][OTf] or Rh-6(CO)(16) to give the four-membered chain tBu(2)PH-BH2-tBu(2)P-BH3 (1), which was isolated in 60%. yield and. characterized by multinuclear NMR spectroscopy, mass spectrometry, and elemental analysis. Thermolysis of 1 in the temperature range 175-180 degreesC led to partial decomposition and the formation of,tBu(2)PH . BH3. When the dehydrocoupling of tBu(2)PH . BH3 was performed in the presence of [{Rh(mu -Cl)(1,5-cod)}2] or RhCl3 hydrate, the chlorinated compound tBu(2)PH-BH2-tBu(2)P-BH2-Cl (2) was formed which could not be obtained free of 1. The molecular structures of tBu(2)PH . BH3, tBu(2)PH-BH2-tBu(2)P-BH3 (1), and tBu(2)PH-BH2-tBu(2)P-BH2Cl (2) together with 1 were determined by single-crystal X-ray diffraction studies.