当前位置: X-MOL 学术Organometallics › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
Reactivity of Fluorinated-Chalcone Phosphines, RPEWO-F4, Induced by C–F Activation upon Coordination to PdCl2
Organometallics ( IF 2.8 ) Pub Date : 2020-03-12 , DOI: 10.1021/acs.organomet.0c00019
Marconi N. Peñas-Defrutos 1 , Andrea Vélez 1 , Pablo Espinet 1
Affiliation  

The E phosphine ligands (R = Ph, o-Tol, Cy), abbreviated as RPEWO-F4, are stable in solution, but they develop a rich reactivity on coordination to PdCl2. The chelate P-olefin coordination to PdCl2 leads eventually to a Z conformation of the fluorinated-chalcone group o-C6F4CH═CHC(O)Ph. From there, a cyclization reaction occurs involving the C═O group and activation of a F atom, yielding a strongly chelated PdCl2(P-carbene) complex. The carbene carbon atom in the complex displays some electrophilicity, which is expressed in hydrolysis, ammonolysis, and oxidation (with peroxide) reactions, affording PdCl2 complexes with new P,C,O-pincer, P,C,N-pincer, or P,O-chelate fluorinated ligands. The C–F activation reactions are slow in comparison to the catalysis rates when the [PdCl2(RPEWO-F4)] complexes have been used in Negishi catalyses. Consequently, the reactivity discussed here is not expected to interfere with the interpretation of the data obtained in Pd-catalytic studies or processes, at least for fast transmetalating nucleophiles.

中文翻译:

氟化活化查尔酮膦RPEWO-F 4的反应性,该活化是由CF活化后与PdCl 2配位引起的

所述ë膦配体(R = PH,Õ -Tol中,Cy),缩写为RPEWO-F 4,是在溶液中稳定,但他们开发上协调丰富的反应性的PdCl 2。螯合的P-烯烃与PdCl 2的配位最终导致氟化查尔酮基o -C 6 F 4 CH = CHC(O)Ph的Z构象。从那里开始发生涉及C═O基团和F原子活化的环化反应,生成强螯合的PdCl 2(P-卡宾)络合物。络合物中的卡宾碳原子显示出一定的亲电性,这表现为水解,氨解和氧化(具有过氧化物)反应,从而提供了具有新的P,C,O钳,P,C,N钳或PdCl 2的络合物。 P,O-螯合物氟化配体。与[PdCl 2(RPEWO-F 4)]络合物用于Negishi催化剂相比,CF活化反应的催化速率慢。因此,至少在快速重金属化亲核试剂方面,预期此处讨论的反应性不会干扰在Pd催化研究或过程中获得的数据的解释。
更新日期:2020-03-12
down
wechat
bug