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Sc and Y Heteroalkyl Complexes with a NCsp3N Pincer‐Type Diphenylmethanido Ligand: Synthesis, Structure, and Reactivity
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2020-08-08 , DOI: 10.1002/ejic.202000306 Ahmad Fayoumi 1 , Dmitry M. Lyubov 2 , Andrey S. Shavyrin 3 , Anton V. Cherkasov 4 , Anatoly M. Ob’edkov 5 , Alexander Trifonov 6 , Alexey O. Tolpygin 7
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2020-08-08 , DOI: 10.1002/ejic.202000306 Ahmad Fayoumi 1 , Dmitry M. Lyubov 2 , Andrey S. Shavyrin 3 , Anton V. Cherkasov 4 , Anatoly M. Ob’edkov 5 , Alexander Trifonov 6 , Alexey O. Tolpygin 7
Affiliation
New diphenylmethane [4‐tBu‐2‐(C3H2N2Me‐1)C6H3]2CH2 (1) bearing pendant imidazolyl groups in ortho‐positions of aromatic rings of diphenylmethane skeleton was synthesized using Stille cross‐coupling reaction between bis(4‐(tert‐butyl)‐2‐iodophenyl)methane and Bu3Sn(C3H2N2Me) in the presence of Pd(PPh3)4. Potassium diphenylmethanide [{[4‐tBu‐2‐(C3H2N2Me‐1)C6H3]2CH}K(OEt2)]2 (2K) was prepared by treatment of 1 with an equimolar amount of Lochmann‐Schlosser super base. Rare‐earth metal heteroalkyl complexes {[4‐tBu‐2‐(C3H2N2Me‐1)C6H3]2CH}Ln(CH2SiMe3)2(THF)n (Ln = Sc, n = 0 (2Sc); Y, n = 1 (2Y)) with NCsp3N pincer type diphenylmethanido ligand were synthesized by the selective sp3 CH‐bond activation of the central CH2 group in 1 by Ln(CH2SiMe3)3(THF)2. According to the X‐ray data the diphenylmethanido ligands in 2K and 2Sc perform a tridentate pincer‐type κ3‐N,C,N coordination. Complexes 2Ln were evaluated as catalysts for isoprene polymerization and hydrosilylation of alkenes and alkynes.
中文翻译:
具有NCsp3N钳型二苯基甲亚胺基配体的Sc和Y杂烷基配合物:合成,结构和反应活性
使用Stille合成了新的二苯甲烷[4 - t Bu-2-(C 3 H 2 N 2 Me-1)C 6 H 3 ] 2 CH 2(1)在二苯甲烷骨架芳环的邻位带有咪唑基侧基在Pd(PPh 3)4存在下,双(4-(叔丁基)-2-碘苯基)甲烷与Bu 3 Sn(C 3 H 2 N 2 Me)之间的交叉偶联反应。二苯甲烷钾[{[4 - t Bu-2-(C 3 H通过用等摩尔量的Lochmann-Schlosser超级碱处理1制备2 N 2 Me-1)C 6 H 3 ] 2 CH} K(OEt 2)] 2(2 K)。稀土金属杂烷基络合物{[4 - t Bu-2-(C 3 H 2 N 2 Me-1)C 6 H 3 ] 2 CH} Ln(CH 2 SiMe 3)2(THF)n(Ln = Sc ,n = 0(2 Sc); Y,n通过使用Ln(CH 2 SiMe 3)3(THF)2对1中的中心CH 2基团进行选择性sp 3 CH键活化反应,合成了具有NC sp3的N钳型二苯基甲酰胺基配体= 1(2 Y)。根据X射线数据在diphenylmethanido配体2 ķ和2钪执行三齿钳型κ 3 -N,C,N的协调。评价了2 Ln的络合物作为异戊二烯聚合以及烯烃和炔烃氢化硅烷化的催化剂。
更新日期:2020-09-09
中文翻译:
具有NCsp3N钳型二苯基甲亚胺基配体的Sc和Y杂烷基配合物:合成,结构和反应活性
使用Stille合成了新的二苯甲烷[4 - t Bu-2-(C 3 H 2 N 2 Me-1)C 6 H 3 ] 2 CH 2(1)在二苯甲烷骨架芳环的邻位带有咪唑基侧基在Pd(PPh 3)4存在下,双(4-(叔丁基)-2-碘苯基)甲烷与Bu 3 Sn(C 3 H 2 N 2 Me)之间的交叉偶联反应。二苯甲烷钾[{[4 - t Bu-2-(C 3 H通过用等摩尔量的Lochmann-Schlosser超级碱处理1制备2 N 2 Me-1)C 6 H 3 ] 2 CH} K(OEt 2)] 2(2 K)。稀土金属杂烷基络合物{[4 - t Bu-2-(C 3 H 2 N 2 Me-1)C 6 H 3 ] 2 CH} Ln(CH 2 SiMe 3)2(THF)n(Ln = Sc ,n = 0(2 Sc); Y,n通过使用Ln(CH 2 SiMe 3)3(THF)2对1中的中心CH 2基团进行选择性sp 3 CH键活化反应,合成了具有NC sp3的N钳型二苯基甲酰胺基配体= 1(2 Y)。根据X射线数据在diphenylmethanido配体2 ķ和2钪执行三齿钳型κ 3 -N,C,N的协调。评价了2 Ln的络合物作为异戊二烯聚合以及烯烃和炔烃氢化硅烷化的催化剂。