摘要
乙酰氯同Fe_3(CO)_(12),RSH,Et_3N所形成的盐[(μ-CO)(μ-RS)Fe_2(CO)_6]Et_3NH相作用,生成一类含醋酸乙烯酯基配体的桥连铁硫配合物(σ,π-μ-CH_3CO_2C=CH_2(μ-RS)Fe_2(CO)_6[R=Et,tert-Bu,Ph)。除用碳氢分析,IR,~1HNMR及X衍射技术表征这类配合物的结构和构象外,还对形成此类产物的过程进行了初步讨论。R=Ph配合物单晶的空间群为PI,晶胞参数a=7.087(3),b=8.824(2),c=15.740(3),α=76.20(1),β=88.15(2),γ=86.28(2)°,D_x=1.65g·cm^(-3),Z=2。醋酸乙烯酯基配体中带有醋酸根的硫与一个铁原子发生σ相互作用,而碳-碳双键与另一个铁原子则发生π相互作用。Fe—Fe键长为2.553(1))苯基与硫桥原子以e键相连。
Unexpectedly, a class of Fe—S complexes containing the ligand of bridging vinylidene acetate(σ, π-μ-CH_3CO_2C=CH_2)(μ-RS)Fe_2(CO)_6(R=Et, tert-Bu, and Ph) were prepared by reaction of acetyl chloride with an active salt of [(μ-CO) (μ-RS)Fe_2(CO)_6]Et_3NH formed from Fe_3(CO)_(12), RSH, and Et_3N. The structures and conformations of these complexes were characterized by elemental analysis. IR, ~1H NMR, and X-ray diffraction techniques and the mechanism of their formation was discussed briefly. The complex with R=Ph is triclinic, belonging to space group P and cell parameters are a=7.087 (3), b= 8.824(2), c=15.740(3); α=76.20(1), β= 88.15(2), γ=86.28(2)°; V=953.8~3; D_x=1.65g·cm^(-3); Z=2; F(000)=476. A kind of σ-interaction occurs between the carbon atom bearing acetate group and one iron atom whereas a π-interaction occurs between carbon—carbon double bond and another iron atom. Bond length of Fo- Fo equals 2.553(1)A and phenyl group is connected to bridging sulfur atom with an e-type of bond.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
1990年第11期1141-1146,共6页
Acta Chimica Sinica
基金
国家自然科学基金
