An isomeric pair of fluoride-bridged cyclic dimolybdenum triads

作者：Cotton F Albert^*; Liu Chun Y; Murillo Carlos A; Zhao Qinliang

来源：Inorganic Chemistry, 2006, 45(23): 9480-9486.

DOI：10.1021/ic061525g

A pair of isomeric cyclic triads containing three quadruply bonded [Mo-2] units, [Mo-2(cis-DAniF)(2)](2+) (DAniF = N, N'-di-p-anisylformamidinate), bridged by six fluoride anions, has been synthesized and crystallographically characterized. For the R isomer, the three [Mo-2] units are oriented in two orthogonal directions. Two of them are structurally equivalent and parallel to each other, but oriented perpendicular to the third one. The beta isomer is a triangle with three geometrically identical [Mo-2] units, parallel to each other, as the vertices. Thus, the beta isomer possesses idealized D-3h symmetry while the alpha isomer only has C-2v symmetry. These two isomers do not interconvert in boiling THF or toluene or under irradiation with ultraviolet light, but oxidation of the alpha isomer first generates an alpha(+) species that changes to beta(+). The two isomers have very similar electrochemical behavior, both showing three reversible one-electron redox processes for the [Mo-2] centers and similar potential separations (Delta E-1/2). The first and second redox couples are well separated (ca. 390-410 mV), while the second and third ones are separated by only about 150 mV.

• 出版日期2006-11-13
• 单位同济大学