Journal of Organometallic Chemistry ( IF 2.3 ) Pub Date : 2021-01-25 , DOI: 10.1016/j.jorganchem.2021.121717 Hsin-Hung Yeh , Ming-Chi Hsu , Yu-Huei Li , Yi-No Hsu , Fang-Yu Shr , Minghuey Shieh
A novel series of ternary antimony–chalcogen iron carbonyl clusters, [{SbTeFe3(CO)9}{Te2Fe3(CO)9}]– (1), [{SbSeFe3(CO)9}{Se2Fe2(CO)6}]– (2), and [{SbSFe3(CO)9}{SFe3(CO)9}]– (3), were synthesized in moderate yields from reactions of [EFe3(CO)9]2– (E = Te, Se, S) with SbCl3. X-ray analyses revealed that complexes 1–3 each can be viewed as a square pyramidal geometry [SbEFe3(CO)9] (E = Te, Se, S), where the Sb atom was further coordinated with pendant cluster fragments [Te2Fe3(CO)9], [Se2Fe2(CO)6], and [SFe3(CO)9], respectively. Interestingly, the oxidation state of the Sb atom in complexes 1–3 was 0, which was evidenced by XPS and XANES. Complexes 1–3 showed high electrophilicity toward a series of metal carbonylates, which produced transmetallated products, the “spiked” square pyramidal complexes [{SbEFe3(CO)9}{M(CO)x}] [M(CO)x = Fe(CO)4, E = Te, 1-Fe; Se, 2-Fe; S, 3-Fe; M(CO)x = Cr(CO)5, Se, 2-Cr; S, 3-Cr] and the Mn(CO)4-bridged di-ESbFe3(CO)9-based clusters [{SbEFe3(CO)9}2Mn(CO)4]– (E = Se, 2-Mn; S, 3-Mn). Furthermore, the diffuse reflectance spectra showed that these ternary and quaternary antimony-chalcogenide metal carbonyl clusters possessed low energy gaps of 0.84–1.48 eV, suggesting possible electron transports within the frameworks, which was supported by crystal packings and DFT calculations.
中文翻译:
三元锑-硫属元素羰基铁配合物及其衍生物:合成,结构,反应性和低能隙特征
一系列新的三元锑-硫族羰基铁簇,[{SbTeFe 3(CO)9 } {Te 2 Fe 3(CO)9 }] –(1),[{SbSeFe 3(CO)9 } {Se 2 Fe 2(CO)6 }] –(2)和[{SbSFe 3(CO)9 } {SFe 3(CO)9 }] –(3)是由[EFe 3(CO)9 ] 2–(E = Te,Se,S)与SbCl 3。透视分析表明,复合物1 - 3的每个可以作为一个方锥体几何[SbEFe被看作3(CO)9 ](E =碲,硒,S),其中的Sb原子,进一步具有侧簇片段协调[特2 Fe 3(CO)9 ],[Se 2 Fe 2(CO)6 ]和[SFe 3(CO)9 ]。有趣的是,在复合物中的锑原子的氧化态1 - 3为0,这是由XPS和XANES证明。配合1 - 3对一系列金属羰基化物表现出高度的亲电性,产生了金属化产物,即“尖峰”方形金字塔络合物[{SbEFe 3(CO)9 } {M(CO)x }] [M(CO)x = Fe(CO)4,E = Te,1-Fe。Se,2-Fe ; S,3-Fe ; M(CO)x = Cr(CO)5,Se,2-Cr;S,3-Cr ]和Mn(CO)4桥接的di-ESbFe 3(CO)9基团簇[{SbEFe 3(CO)9 } 2 Mn(CO)4 ]–(E = Se,2-Mn; S,3-Mn)。此外,漫反射光谱表明,这些三元和四元硫族硫属金属羰基簇具有0.84–1.48 eV的低能隙,表明在框架内可能存在电子传输,这由晶体堆积和DFT计算支持。