Reaction of a P/Al-Based Frustrated Lewis Pair with Ammonia, Borane, and Amine-Boranes: Adduct Formation and Catalytic Dehydrogenation
Reaction of a P/Al-Based Frustrated Lewis Pair with Ammonia, Borane, and Amine-Boranes: Adduct Formation and Catalytic Dehydrogenation
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DOI：
10.1002/anie.201208746
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发表时间：
2013-01-01
影响因子：
16.6
通讯作者：
Uhl, Werner
中科院分区：
文献类型：
--
作者：
Appelt, Christian;Slootweg, J. Chris;Uhl, Werner
过渡金属中心单键活化的发现导致了大量的催化转化，这凸显了有机金属化学的力量。最近，主基团系统，[1]，如基于B/ p的受挫刘易斯对（FLPs）[2]和单线态碳烯，[3]，拥有一个孤电子对和一个空轨道，也被证明能够分裂化学键。然而，尽管在主基团化学方面取得了重大进展，但将活化片段转移到底物上仍然具有挑战性。困难在于再生活性物质，这是催化转化的必要条件。到目前为止，已知FLP的催化作用仅与共价HÀH[4]和SiÀH[5,6]键和氢化钠[7]我们很想延续这个系列。由于FLPs对硼烷和胺的异裂解BÀH[9]和NÀH[10]键的激活很少受到关注，因此我们研究了活化物质2,3a与加合物2,3b的形成（方案1）。为此，我们将易于获得的双磷/铝基flp1[11]与BH3·THF、氨（NH3）和胺硼烷H3B·NR2H [12]（R= H和Me）反应。在过渡-中揭示了B/N加合物作为载氢载体的潜力
The discovery of single-bond activation at transition-metal centers has led to a plethora of catalytic transformations, which highlights the power of organometallic chemistry. Recently, main-group systems,[1] such as B/P-based frustrated Lewis pairs (FLPs)[2] and singlet carbenes,[3] possessing a lone pair of electrons and a vacant orbital were also shown to be able to split chemical bonds. Yet, despite this major advancement in main-group chemistry, the transfer of an activated fragment to a substrate remains challenging. The difficulty lies in regenerating the active species, which is a necessity for catalytic turnover. So far, FLP catalysis is only known with covalent HÀH [4] and SiÀH [5, 6] bonds and sodium hydride.[7] We were keen to extend this series.[8]Because the heterolytic BÀH [9] and NÀH [10] bond activation of boranes and amines by FLPs has received little attention, we investigated the formation of the activated species 2, 3A versus the adducts 2, 3B (Scheme 1). For this, we reacted the readily accessible geminal phosphorus/aluminumbased FLP 1 [11] with BH3· THF, ammonia (NH3), and amine–boranes H3B· NR2H [12](R= H and Me). The potential of the B/N adduct as hydrogen carrier was revealed in the transition-