Alkene metatheses in transition metal coordination spheres: dimacrocyclizations that join trans positions of square-planar platinum complexes to give topologically novel diphosphine ligands
作者:Takanori Shima、Eike B. Bauer、Frank Hampel、J. A. Gladysz
DOI:10.1039/b400156g
日期:——
phosphines PPh((CH2)(n)CH=CH2)2)2 are prepared from PPhH(2), n-BuLi, and the corresponding bromoalkenes (1:2:2), and combined with the platinum tetrahydrothiophene complex [Pt(mu-Cl)(C(6)F(5))(S(CH2CH2(-))2)]2 to give the square-planar adducts trans-(Cl)(C(6)F(5))Pt(PPh((CH2)(n)CH=CH2)2)2 (11, 93-73%; n=a, 2; b, 3; c, 4; d, 5; e, 6; f, 8). Ring-closing metatheses with Grubbs' catalyst (2) are studied
由PPhH(2),n-BuLi和相应的溴代烯烃(1:2:2)制备含烯烃的膦PPh((CH2)(n)CH = CH2)2)2,并与四氢噻吩铂结合络合物[Pt(mu-Cl)(C(6)F(5))(S(CH2CH2(-))2)] 2给出方平面加合物反式-(Cl)(C(6)F(5 ))Pt(PPh((CH2)(n)CH = CH2)2)2(11,93-73%; n = a,2; b,3; c,4; d,5; e,6; f ,8)。研究了用Grubbs催化剂(2)进行的闭环复分解反应。氢化后,分离出两个反式-(Cl)(C6F5)[式:见正文](14)Ph)(15e)的异构体。两者都通过反膦配体之间的双大环形成,但在PPh环的位置上有所不同(syn,31%;抗,7%)。通过(i)保护作为硼烷加合物H(3)B的4e独立地制备替代的配体内复分解产物反式-(C1)(C6F5)[式:参见文本](14)Ph)2(