A series of Ln(III) tris(benzhydryl) complexes [(p‐tBu‐C₆H₄)₂CH]₃Ln (Ln=La (1), Nd (2), Y (3)) were synthesized by the salt metathesis reactions of LnHal₃(THF)_3.5 (Ln=La, Nd, Hal=Cl; Ln=Y, Hal=I) and [(p‐tBu‐C₆H₄)₂CH]Na. In 1–3 the benzhydryl ligands are linked with the metal centres in η⁴‐coordination mode. For diamagnetic complexes 1 and 3 a fluxional behaviour was detected in solution. Complexes 1–3 proved to be thermally stable: no decomposition was observed even after heating their solutions in toluene‐d₈ at 140 °C during 72 h. The reactions of 1 and 2 with B(C₆F₅)₃ allowed for the synthesis of base‐free cationic complexes [(p‐tBu‐C₆H₄)₂CH]₂Ln[(p‐tBu‐C₆H₄)₂CHB(C₆F₅)₃] (Ln=La (4), Nd (5)) which adopt the structure of a contact ion pair. Combinations of 1–3 and borane ((B(C₆F₅)₃, [Me₂NHPh][B(C₆F₅)₄], [Ph₃C][B(C₆F₅)₄]) as well as 4 and 5 were found to be highly efficient, regio‐ and chemoselective catalysts for hydroarylation and hydrobenzylation of C=C bonds of a variety of substrates with substituted pyridines. These catalysts enable highly challenging transformations such as hydrobenzylation of 1,1‐disubstituted and internal C=C bonds.

中文翻译：

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三（苯甲酰基）和阳离子双（苯甲酰基）Ln（III）配合物：烯烃加氢芳基化和吡啶取代的苄基化中出色的热稳定性和催化活性

一系列LN（III）的三（二苯甲基）配合物[（p -吨卜-C ₆ H ^ ₄）₂ CH] ₃ LN（Ln为La（上1），钕（2），Y（3））是由合成LnHal的盐复分解反应₃（THF）_3.5（Ln为镧，钕，哈尔=氯; Ln为Y，哈尔= I）和[（p -吨卜-C ₆ H ^ ₄）₂ CH]的Na。在1-3的二苯甲基的配体与金属中心连接的η ⁴ -coordination模式。对于抗磁性配合物1和3在溶液中检测到fluxional行为。配合物1 - 3被证明是热稳定的：即使在甲苯-d加热它们的溶液后，没有观察到分解₈ 72小时期间在140℃下。的反应1和2与B（C ₆ ˚F ₅）₃允许游离碱阳离子络合物的合成[（p -吨卜-C ₆ H ^ ₄）₂ CH] ₂ LN [（p -吨卜-C ₆高₄）₂CHB（C ₆ F ₅）₃ ]（Ln ＝ La（4），Nd（5））采用接触离子对的结构。组合1 - 3和硼烷（（B（C ₆ ˚F ₅）₃，[我₂ NHPh基] [B（C ₆ ˚F ₅）₄ ]，[PH ₃ C] [B（C ₆ ˚F ₅）₄ ]）以及4和5被发现是高效的区域和化学选择性催化剂，可用于各种具有取代吡啶的底物的C = C键进行氢芳基化和加氢苄基化。这些催化剂能够实现极富挑战性的转化，例如1,1-二取代和内部C = C键的加氢苄基化。