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New reactivity patterns in 3H-phosphaallene chemistry [Aryl-P=C=C(H)-tBu] - hydroboration of the C=C bond, deprotonation and trimerisation.
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2020-07-03 , DOI: 10.1002/chem.202002506
Jonas C Tendyck 1 , Alexander Hepp 1 , Ernst-Ulrich Würthwein 2 , Werner Uhl 1
Affiliation  

3H‐Phosphaallenes, R−P=C=C(H)C−R’ (3), are accessible in a multigram scale on a new and facile route and show a fascinating chemical reactivity. BH3(SMe2) and 3 a (R=Mes*, R’=tBu) afforded by hydroboration of the C=C bonds of two phosphaallene molecules an unprecedented borane (7) with the B atom bound to two P=C double bonds. This compound represents a new FLP based on a B and two P atoms. The increased Lewis acidity of the B atom led to a different reaction course upon treatment of 3 a with H2B‐C6F5(SMe2). Hydroboration of a C=C bond of a first phosphaallene is followed in a typical FLP reaction by the coordination of a second phosphaallene molecule via B−C and P−B bond formation to yield a BP2C2 heterocycle (8). Its B−P bond is short and the B‐bound P atom has a planar surrounding. Treatment of 3 a with tBuLi resulted in deprotonation of the β‐C atom of the phosphaallene (9). The Li atom is bound to the P atom as demonstrated by crystal structure determination, quantum chemical calculations and reactions with HCl, Cl‐SiMe3 or Cl‐PtBu2. The thermally unstable phosphaallene Ph−P=C=C(H)‐tBu gave a unique trimeric secondary product by P−P, P−C and C−C bond formation. It contains a P2C4 heterocycle and was isolated as a W(CO)4 complex with two P atoms coordinated to W (15).

中文翻译:

在3H-磷杂戊烯化学中的新反应模式[芳基-P = C = C(H)-tBu]-C = C键的硼氢化,去质子化和三聚。

3H-苯丙三环,R-P = C = C(H)C-R'(3),可在新的便捷途径上以克数形式获得,并显示出令人着迷的化学反应性。BH 3(SMe 2)和3a(R = Mes *,R'= t Bu)是通过氢硼化两个磷丙二烯分子的C = C键而得到的,这是前所未有的硼烷(7),其中B原子键合到两个P = C双键。该化合物代表一个基于B和两个P原子的新FLP。增加治疗后导致了不同的反应过程中的乙原子的路易斯酸性3用H 2 B-C 6 ˚F 5(SME 2)。在典型的FLP反应中,第一磷杂丙烯的C = C键进行氢硼化之后,第二磷杂丙烯分子通过BC和P-B键形成配位基团,生成BP 2 C 2杂环(8)。它的BP键很短,且B结合的P原子有一个平面包围。用t BuLi处理3 a导致磷丙二烯的β-C原子去质子化(9)。如晶体结构测定,量子化学计算以及与HCl,Cl-SiMe 3或Cl-P t Bu 2的反应所示,Li原子与P原子结合。热不稳定磷杂丙烯Ph-P = C = C(H)-tBu通过P-P,P-C和C-C键的形成给出了独特的三聚体二级产物。它包含一个P 2 C 4杂环,被分离为W(CO)4配合物,其中两个P原子与W(15)配位。
更新日期:2020-07-03
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