六核钴原子簇化学 3: 一些含Co~6八面体簇骼的原子簇化合物的合成、结构和电化学性质

(R~8P)~4-nCoX~n(R=Ph,Et 等;X=C,B=1,2)与Na~E~x(E=S,Se;X=1,2)在DMF或DMF/乙醇介质中反应得到了一系列六核钴的原子簇化合物Co~6(μ~3-E)~8(PR~3)~6.这些化合物含有正规的或畸变的Co~6八面簇骼.化合物可以用I~2氧化生成正一价的簇合物而不改变簇骼的几何构型,反达来,正一价的簇合物也可以被苊烯钠还生成中性的簇合物.本文还研究了这些化合物的电化学性质并提出了氧化还原反应的电子传递过程.

The chemistry of hexacobalt cluster compounds pt.3:syntheses,structures and electrochemical properties of a series of hexacobalt cluster compounds with octahedral Co~6 cores

The reaction of (R3P)4-nCoXn (R = Ph, Et; X = Cl, Br; n = 1, 2) with Na2Ex (E = S, Se; x = 1, 2) in DMF or DMF/EtOH solution gave the hexacobalt cluster compounds, Co6(m3-E)8(PR3)6 (I), in high yields. The mol. structures of the compounds consist of regular or distorted Co6 octahedra. The neutral compounds I can be oxidized by I2 to form monocationic species with no change to the Co6 octahedral cores, while the monocationic compounds, Co6(m3-E)8(PR3)6]+, can be reduced by sodium acenaphthalenide to form neutral species. Electrochem. properties of the compounds in CH2Cl2 were studied and electron-transfer sequences for the compounds were also described.