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首页> 外文期刊>Organometallics >Synthesis, structure, and electrochemical studies of mu(3)-eta(2),eta(2),eta(2)-C-60 triosmium complexes
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Synthesis, structure, and electrochemical studies of mu(3)-eta(2),eta(2),eta(2)-C-60 triosmium complexes

机译:mu(3)-eta(2),eta(2),eta(2)-C-60 os络合物的合成,结构和电化学研究

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Two mu(3)-eta(2),eta(2),eta(2)-C-60 complexes, Os-3(CO)(8)(PPh3)(mu(3)-eta(2),eta(2),eta(2)-C-60) (8) and Os-3(CO)(7)(PMe3)(2)(mu(3)-eta(2),eta(2),eta(2)-C-60) (9), have been prepared by decarbonylation of Os-3(CO)(9)(mu(3)-eta(2),eta(2),eta(2)-C-60) (6) with Me3NO/MeCN in the presence of phosphine ligands. The molecular structure of 8 has been determined by a single-crystal X-ray diffraction study. The structure of 8 is derived from that of Os-3(CO)(11)(PPh3) by replacing three axial carbonyl ligands with a mu(3)-face-capping C-6 ring of C-60. The C-13 NMR spectra (C-60 region) of 6 and Os-3(CO)(8)(PMe3)(mu(3)-eta(2),eta(2),eta(2)-C-60) (7) show 11 sp(2) and 1 sp(3) carbon resonances and 29 sp(2) and 3 sp(3) carbon resonances, respectively, which are consistent with C-3v and C-s symmetric nature of the two complexes in solution. Electrochemical properties of 6, 7, and 9 have been studied by cyclic voltammetry (CV) in 1,2-dichlorobenzene (DCB) solutions. The general features of CV curves have revealed four reversible redox couples for 6 and 7 and three for 9 in the DCB potential window. The mu(3)-eta(2),eta(2),eta(2)-C-60 complexes, 6, 7, and 9, show a remarkable electrochemical stability compared to the known eta(2)-C-60 triosmium carbonyl complexes. The CV results suggest that a C-60-mediated electron transfer to the triosmium center takes place in 6 and 7, but three successive C-60-localized reductions occur in 9. [References: 26]
机译:两个mu(3)-eta(2),eta(2),eta(2)-C-60复合物,Os-3(CO)(8)(PPh3)(mu(3)-eta(2),eta (2),eta(2)-C-60)(8)和Os-3(CO)(7)(PMe3)(2)(mu(3)-eta(2),eta(2),eta( 2)-C-60)(9)是通过Os-3(CO)(9)(mu(3)-eta(2),eta(2),eta(2)-C-60脱羰而制得的)(6)在膦配体存在下用Me3NO / MeCN。 8的分子结构已通过单晶X射线衍射研究确定。 8的结构源自Os-3(CO)(11)(PPh3)的结构,方法是将三个轴向羰基配体替换为C-60的具有mu(3)面封盖的C-6环。 6和Os-3(CO)(8)(PMe3)(mu(3)-eta(2),eta(2),eta(2)-C-的C-13 NMR光谱(C-60区域) 60)(7)分别显示11 sp(2)和1 sp(3)碳共振以及29 sp(2)和3 sp(3)碳共振,这与两者的C-3v和Cs对称性质一致溶液中的配合物。已通过循环伏安法(CV)在1,2-二氯苯(DCB)溶液中研究了6、7和9的电化学性质。 CV曲线的一般特征在DCB电位窗口中显示了6和7的四个可逆氧化还原对和9的三个可逆氧化还原对。 mu(3)-eta(2),eta(2),eta(2)-C-60配合物6、7和9与已知的eta(2)-C-60相比显示出显着的电化学稳定性羰基络合物。 CV结果表明,在60和7中发生了C-60介导的电子转移到tri中心,但在9中发生了三个连续的C-60局部还原。[参考文献:26]

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