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首页> 外文期刊>Journal of chemical crystallography >X-ray structure and redox chemistry of the heptacobalt cluster Co-3(CO)(9)[mu(3)-CCO2CH2CCH{Co-4(CO)(10)}]
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X-ray structure and redox chemistry of the heptacobalt cluster Co-3(CO)(9)[mu(3)-CCO2CH2CCH{Co-4(CO)(10)}]

机译：七钴簇Co-3（CO）（9）[mu（3）-CCO2CH2CCH {Co-4（CO）（10）}]的X射线结构和氧化还原化学

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摘要

The tetrahedrane cluster Co-3(CO)(9)(mu(3)- CCO2CH2C dropCH) reacts with Co-4( CO)(12) to furnish the heptacobalt compound Co-3(CO)(9)[mu(3) - CCO2CH2CCH{Co-4(CO)(10)}] in high yield. Substitution of the pendant alkyne group by the Co-4(CO)(10) moiety was ascertained by IR and H-1 NMR spectroscopies, and the solid- state structure of Co-3(CO)(9)[ mu(3) -CCO2CH2CCH{Co-4( CO)(10)}] was unequivocally determined by X- ray crystallography. Co-3(CO)(9)[mu(3)- CCO3CH3CCH{Co-4(CO)(10)}] crystallizes in the monoclinic space group P2(1), a = 12.895(13) Angstrom, b = 18.803(18) Angstrom, c = 13.748(13) Angstrom, beta = 97.27(2)degrees, V = 3307(6) Angstrom(3), Z = 4, d(calc) = 2.087 mg/m(3); R = 0.0493, R-w = 0.0989 for 4310 observed reflections with I > 2sigma(I). The X- ray structure confirms the presence of an intact tetrahedral Co-3 moiety and an alkyne- tethered Co-4 butterfly cluster moiety. The cyclic voltammetric properties of Co-3(CO)(9)[mu(3)-CCO2CH2CCH{Co-4(CO)(10)}] were examined and three reduction waves were found. The first two reduction waves correspond to the regionally localized 0/1(-) redox couples on the tetra- and tricobalt moieties, respectively, while the third redox process is assigned to the 1(-)/2(-) reduction associated with the tetracobalt residue. Both 0/1(-) redox couples are reversible, while the 1(-)/2(-) reduction exhibits only quasi- reversible behavior. No evidence for electronic communication between the Co-3 and Co-4 portions of the complex was observed. Extended Huckel MO calculations support the site of the first reduction occurring solely on the tetracobalt moiety of this Co-7 cluster. [References: 27]
机译：四面体簇Co-3（CO）（9）（mu（3）-CCO2CH2C dropCH）与Co-4（CO）（12）反应生成七钴化合物Co-3（CO）（9）[mu（3） ）-高收率的CCO2CH2CCH {Co-4（CO）（10）}]。通过IR和H-1 NMR光谱法确定Co-4（CO）（10）部分取代的炔基侧基，以及Co-3（CO）（9）[mu（3））的固态结构-CCO2CH2CCH {Co-4（CO）（10）}]的确通过X射线晶体学确定。 Co-3（CO）（9）[mu（3）-CCO3CH3CCH {Co-4（CO）（10）}]在单斜空间群P2（1）/ n中结晶，a = 12.895（13）埃，b = 18.803（18）埃，c = 13.748（13）埃，beta = 97.27（2）度，V = 3307（6）埃（3），Z = 4，d（计算）= 2.087 mg / m（3） ; R = 0.0493，对于I> 2sigma（I）观察到的4310个反射，R-w = 0.0989 X射线结构证实了完整的四面体Co-3部分和炔烃连接的Co-4蝴蝶簇部分的存在。检查了Co-3（CO）（9）[mu（3）-CCO2CH2CCH {Co-4（CO）（10）}]的循环伏安特性，发现了三个还原波。前两个还原波分别对应于四-和三叶草部分上的局部本地化的0/1（-）氧化还原对，而第三次氧化还原过程被分配给与还原相关的1（-）/ 2（-）还原。四钴残基。两个0/1（-）氧化还原对都是可逆的，而1（-）/ 2（-）还原仅表现出准可逆的行为。没有观察到复合物的Co-3和Co-4部分之间进行电子通讯的证据。扩展的Huckel MO计算支持仅在此Co-7簇的四钴部分上发生的第一次还原的位点。 [参考：27]

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