Synthesis and Properties of<i>s</i>-Alkyl-Substituted Silanediyl-Bridged and Silanetriyl-Bridged Diiron Complexes, Cp<sub>2</sub>(CO)<sub>2</sub>Fe<sub>2</sub>(<i>μ</i>-CO)[<i>μ</i>-Si(X)CHR<sub>2</sub>] and Cp<sub>2</sub>(CO)<sub>2</sub>Fe<sub>2</sub>(<i>μ</i>-CO)[<i>μ</i>-Si(DMAP)CHR<sub>2</sub>]<sup>+</sup>I<sup>−</sup>(X = H, I; R = Et, Ph; DMAP = 4-(Dimethylamino)pyridine)
Cp2(CO)2Fe2(μ-CO)[μ-Si(I)CHR2] (4a: R = Et; 4b: R = Ph) in cis-form. The reaction of complexes 4 with 4-(dimethylamino)pyridine (= DMAP) gives the base-stabilized silylyne (or silanetriyl)-bridged diiron complexes Cp2(CO)2Fe2(μ-CO)[μ-Si(DMAP)CHR2]+I− (5a: R = Et; 5b: R = Ph) in 35 and 43% yields, respectively. The cis–transisomerization of complexes 3 was studied under thermal and photochemical reaction conditions
2 摩尔量的 CpFe(CO)2SiMe3 (= FpSiMe3, 1) 与 s-烷基硅烷 R2CHSiH3 (2a: R = Et; 2b: R = Ph) 光解产生亚甲硅烷 (或硅烷二基)-桥连二铁配合物 Cp2(CO) 2Fe2(μ-CO)[μ-Si(H)CHR2] (3a: R = Et; 3b: R = Ph) 主要以顺式形式存在。用过量的 CH2I2 立体选择性地处理 cis-3 得到碘亚硅烷桥连的二铁配合物 Cp2(CO)2Fe2(μ-CO)[μ-Si(I)CHR2] (4a: R = Et; 4b: R = Ph) 顺式。配合物 4 与 4-(二甲氨基)吡啶 (= DMAP) 反应得到碱稳定的甲硅烷基(或硅烷三基)桥连二铁配合物 Cp2(CO)2Fe2(μ-CO)[μ-Si(DMAP)CHR2]+ I− (5a: R = Et; 5b: R = Ph) 分别为 35% 和