The structure of the latter was determined by X-ray crystallography. The loss of oxygen can be suppressed by performing the acylation-elimination sequence in the presence of poly-(4-vinylpyridine). This provided a selective access to complexes of Z-sulfines, [CpRu(PMe3)2(O=S=CHR)]PF6 (R = Ph, 4-C6H4Cl) and [CpRu(dppm)(O=S=CHR)]PF6 (R = Ph, 4-C6H4Cl, COOEt, Cl). Complexes of the parent sulfine O=S=CH2
摘要 阳离子
钌亚砜配合物[CpRu(PR´3)2(O=S=CHR)]PF6 已通过多种方法获得。
硫醛复合物 [CpRu(PR´3)2(S=CHR)]PF6 与 2-tosyl-3-phenyl-oxaziridine (PR´3 =
PMe3) 或
单过氧邻苯二甲酸镁 (PR´3 = 1/2) 的
氧化dp
PM) 以热力学不太稳定的 E 形式选择性地得到芳基
亚砜 (R = Ph, 3-
C6H4F, 4-
C6H4Cl, 4-C6H4OMe) 的配合物。从亚
磺酸根络合物 [CpRu(
PMe3)2(SO2CHRSiMe3)] 中消除
硅氧烷,产生
脂肪族亚
磺酸的复合物 [CpRu(
PMe3)2(O=S=CHR)]PF6 (R=H,Me)。用
乙酰氯处理 [CpRu(dp
PM)(SO2 R)] 导致
氧重新分布,产生
硫醛复合物 [CpRu(dp
PM)(η2-S=
CH2)]PF6 和 [CpRu(dp
PM)(η1-S=CHR)