A lanthanum amide complex, La(L)[N(SiHMe₂)₂](thf) (L = N,N″-bis(pentafluorophenyl)diethylenetriamine dianion, 1a), upon activation with B(3,4,5-F₂C₆H₂)₃ (2a), showed excellent catalytic activity for N-methylation of N-alkylaniline derivatives with CO₂ in the presence of PhSiH₃. A catalytically active lanthanum hydridotriarylborate complex, [La(L)(thf)₂][HB(3,4,5-F₃C₆H₂)₃] (5aa), was generated via hydride abstraction from the Si–H moiety of 1a by moderate Lewis acid 2a in THF. DFT studies of the CO₂ hydrosilylation step clarified the following multiple noncovalent interactions as key factors for locating the HB(3,4,5-F₂C₆H₂)₃ anion and B(3,4,5-F₃C₆H₂)₃ near the lanthanum center in the transition states of CO₂ reduction and Si–O bond formation: (1) π–π interaction between the electron-deficient C₆F₅ ring on ligand L and the 3,4,5-F₃C₆H₂ ring of the HB(3,4,5-F₃C₆H₂)₃ anion and (2) C–H···F hydrogen bonds between the ortho-C–H bond of B(3,4,5-F₃C₆H₂)₃ and the fluorine atoms of L.

中文翻译：

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含氮三齿配体的氢化三芳基硼酸镧配合物催化苯胺衍生物与 CO2 和苯基硅烷的 N-甲基化

镧酰胺络合物，La( L )[N(SiHMe ₂ ) ₂ ](thf) ( L = N , N ″-bis(pentafluorophenyl)diethylenetriamine dianion, 1a )，用 B(3,4,5-F 活化₂ C ₆ H ₂ ) ₃ ( 2a )在PhSiH ₃存在下对CO _2对N-烷基苯胺衍生物的N-甲基化表现出优异的催化活性。催化活性氢化三芳基硼酸镧络合物，[La( L )(thf) ₂ ][HB(3,4,5-F₃ C ₆ H ₂ ) ₃ ] ( 5aa ) 是由中等路易斯酸2a在 THF 中通过氢化物从1a的 Si-H 部分中提取而生成的。_{CO 2}氢化硅烷化步骤的 DFT 研究阐明了以下多种非共价相互作用是定位 HB(3,4,5-F ₂ C ₆ H ₂ ) ₃阴离子和 B(3,4,5-F ₃ C ₆的关键因素H ₂ ) _{3在CO 2}的过渡态中靠近镧中心还原和 Si-O 键形成： (1)配体L上的缺电子 C ₆ F ₅环与 HB(3,4)的 3,4,5-F ₃ C ₆ H ₂环之间的 π-π 相互作用,5-F ₃ C ₆ H ₂ ) ₃阴离子和B(3,4,5-F ₃ C ₆ H ₂ ) _3的邻-C-H键之间的(2) C-H···F氢键和L的氟原子。