Thermally Stable Half-Sandwich Benzhydryl Ln(II) (Ln = Sm, Yb) Complexes Supported by Sterically Demanding Carbazolyl and Fluorenyl Ligands,Organometallics

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Thermally Stable Half-Sandwich Benzhydryl Ln(II) (Ln = Sm, Yb) Complexes Supported by Sterically Demanding Carbazolyl and Fluorenyl Ligands
Organometallics ( IF 2.5 ) Pub Date : 2019-12-03 , DOI: 10.1021/acs.organomet.9b00624
Alexander N. Selikhov _{1,

2} , Andrey S. Shavyrin ₁ , Anton V. Cherkasov ₁ , Georgy K. Fukin ₁ , Alexander A. Trifonov _{1,

2}

Affiliation

A series of new isolable and thermally stable half-sandwich Ln(II) benzhydryl complexes coordinated by the sterically demanding ligands tert-butylcarbazol-9-yl [tBu₄Carb]Ln[(p-tBu-C₆H₄)₂CH](L) (Ln = Sm, L = DME (4); Ln = Yb, L = DME (5); Ln = Yb, L = TMEDA (6)) and 2,7-di-tert-butyl-fluoren-9-trimethylsilylyl [2,7-tBu₂-9-Me₃Si-C₁₃H₆]Yb[(p-tBu-C₆H₄)₂CH](DME) (7) were synthesized by the alkane elimination reaction of [(p-tBu-C₆H₄)₂CH]₂Ln(L_n) (Ln = Sm, Yb) with tBu₄CarbH and 2,7-tBu₂-9-Me₃Si-C₁₃H₇. X-ray analysis revealed that in 4, 5, and 7 the benzhydryl ligand is coordinated to the metal ion in an η³ coordination mode, while in 6 it is η¹-bound. The type of coordination of the benzhydryl ligands in diamagnetic 5–7 is retained in their C₆D₆ solutions. Complexes 4–7 demonstrated unprecedented thermal stability and do not undergo decomposition after heating their solutions in C₆D₆ or toluene at 100 °C for 72 h. The reactions of [tBu₄Carb]Ln[(p-tBu-C₆H₄)₂CH](DME) (Ln = Sm (4), Ln = Yb (5)) with an excess of DME led to the formation of the symmetrical bis(carbazolyl) complex products [tBu₄Carb]₂Ln(DME)₄ (Ln = Sm (8), Yb (9)) isolated in the form of separated ion pairs.

中文翻译：

热稳定的半三明治式苯甲酰基Ln（II）（Ln = Sm，Yb）配合物，由立体要求的咔唑基和芴基配体支持

一系列新的可分离且热稳定的半三明治Ln（II）苯二甲酰配合物，由立体要求高的配体叔丁基咔唑-9-基[ t Bu ₄ Carb] Ln [（p - t Bu-C ₆ H ₄）_2配位CH]（L）（Ln = Sm，L = DME（4）; Ln = Yb，L = DME（5）; Ln = Yb，L = TMEDA（6））和2,7-二叔丁基-芴-9-基trimethylsilylyl [2,7-吨卜₂ -9-ME ₃的Si-C ₁₃ H ^ ₆ ]镱[（p -吨卜-C通过[（pt Bu-C ₆ H ₄）₂ CH] ₂ Ln（L _n）（Ln = Sm，Yb）与t Bu的烷烃消除反应合成₆ H ₄）₂ CH]（DME）（7）₄ CarbH和2,7 - t Bu ₂ -9-Me ₃ Si-C ₁₃ H ₇。X射线分析表明，在4，5，和7的二苯甲基配位体配位到在η与金属离子³配位模式，而在6它是η ^1分结合的。在抗磁二苯甲基配位体的配位类型5 - 7被保持在它们的C ₆ d ₆解决方案。配合物4 – 7具有前所未有的热稳定性，并且将其在C ₆ D ₆或甲苯中的溶液在100°C下加热72小时后不会分解。[ t Bu ₄ Carb] Ln [（p - t Bu-C ₆ H ₄）₂ CH]（DME）（Ln = Sm（4），Ln = Yb（5））与过量的DME导致形成对称的双（咔唑基）复杂产物[ t Bu ₄ Carb] ₂ Ln（DME）₄（Ln = Sm（8），Yb（9）），形式为分离的离子对。

更新日期：2019-12-04

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