The Electron Transfer Series [MoIII(bpy)3]n (n=3+, 2+, 1+, 0, 1−), and the Dinuclear Species [{MoIIICl(Mebpy)2}2(μ2‐O)]Cl2 and [{MoIV(tpy.)2}2(μ2‐MoO4)](PF6)2⋅4 MeCN |
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| Authors: | Dr Mei Wang Dr Thomas Weyhermüller Prof Karl Wieghardt |
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| Institution: | Max Planck Institute for Chemical Energy Conversion, Stiftstrasse 34‐36, 45470 Mülheim an der Ruhr (Germany), Fax: (+49)?208‐306‐3952 |
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| Abstract: | The electronic structures of the five members of the electron transfer series Mo(bpy)3]n (n=3+, 2+, 1+, 0, 1?) are determined through a combination of techniques: electro‐ and magnetochemistry, UV/Vis and EPR spectroscopies, and X‐ray crystallography. The mono‐ and dication are prepared and isolated as PF6 salts for the first time. It is shown that all species contain a central MoIII ion (4d3). The successive one‐electron reductions/oxidations within the series are all ligand‐based, involving neutral (bpy0), the π‐radical anion (bpy.)1?, and the diamagnetic dianion (bpy2?)2?: MoIII(bpy0)3]3+ (S=3/2), MoIII(bpy.)(bpy0)2]2+ (S=1), MoIII(bpy.)2(bpy0)]1+ (S=1/2), MoIII(bpy.)3] (S=0), and MoIII(bpy.)2(bpy2?)]1? (S=1/2). The previously described diamagnetic dication “MoII(bpy0)3](BF4)2” is proposed to be a diamagnetic dinuclear species {Mo(bpy)3}2(μ2‐O)](BF4)4. Two new polynuclear complexes are prepared and structurally characterized: {MoIIICl(Mebpy0)2}2(μ2‐O)]Cl2 and {MoIV(tpy.)2}2(μ2‐MoVIO4)](PF6)2?4 MeCN. |
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| Keywords: | electrochemistry ligand effects molybdenum noninnocent ligands X‐ray diffraction pi‐radical ligands |
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