Cycloruthenated Complexes from Iminophosphoranes: Synthesis, Structure, and Reactivity with Internal Alkynes
Cycloruthenated Complexes from Iminophosphoranes: Synthesis, Structure, and Reactivity with Internal Alkynes
复制标题
DOI：
10.1021/om100997x
复制
发表时间：
2011-02-14
期刊：
影响因子：
2.8
通讯作者：
Urriolabeitia, Esteban P.
中科院分区：
文献类型：
--
作者：
Aguilar, David;Bielsa, Raquel;Urriolabeitia, Esteban P.
通过Hg（C6 H4 - 2-PPh 2 =NR）（2）衍生物与[（eta（6）-arene）Ru（mu-Cl）Cl]（2）的金属转移反应，合成了含邻位取代亚氨基磷杂环戊烷的环钌化配合物[（eta（6）-arene）Ru（C6 H4 -2-PPh 2 = NR）Cl]（arene =苯，对伞花烃; R = Ph，H）.这些配合物与内炔R1 CR2（R-1，R-2 = Ph，Et，CO2 Me），KPF 6和CuBr 2反应干净，生成1，1，2-三苯基-3，4-二（烷基/芳基）-2，1 λ（5）-苯并氮杂磷杂-2-鎓杂环[C6 H4-PPh 2-NPh-C（R-1）=C（R-2）-3，4]（+）的PF 6盐。在所有研究的情况下，只观察到单插入产物。在不对称炔MeC CPh的情况下，插入是区域选择性的，并且得到[C6 H4-PPh 2-NPh-C（Me）=C（Ph）-3，4-PF 6盐。
Cycloruthenated complexes [(eta(6)-arene)Ru(C6H4-2-PPh2=NR)Cl] (arene = benzene, p-cymene; R = Ph, H) containing orthometalated iminophosphoranes have been obtained by transmetalation reactions from Hg(C6H4-2-PPh2=NR)(2) derivatives to [(eta(6)-arene)Ru(mu-Cl)Cl](2). These complexes react cleanly with internal alkynes R1C CR2 (R-1, R-2 = Ph, Et, CO2Me), KPF6, and CuBr2, yielding the 1,1,2-triphenyl-3,4-di(alkyl/aryl)-2, 1 lambda(5)-benzazaphosphinin-2-ium heterocycles [C6H4-PPh2-NPh-C(R-1)=C(R-2)-3,4](+) as PF6 salts. In all studied cases only the monoinsertion products have been observed. In the case of the asymmetric alkyne MeC CPh the insertion is regioselective, and the [C6H4-PPh2-NPh-C(Me)=C(Ph)-3,4]PF6 salt is obtained.