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CpCo(dithiolene) complexes of highly flexible oxddt ligand with two different Z-shaped and U-shaped structures
Authors:Mitsushiro Nomura  Daisuke Takeuchi
Institution:Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, 7-1, Kioi-cho, Chiyoda-ku, Tokyo 102-8554, Japan
Abstract:CpCo(oxddt)] complex (2, oxddt = o-xylenediyldithioethylene-1,2-dithiolate, Cp = η5-cyclopentadienyl) was obtained from o-xylenediyldithioethylene-1,3-dithiol-2-one (Odouble bond; length as m-dashC(oxddt)) (1). 2 further reacted with diazoalkanes (N2CHR) to form some alkylidene-bridged adducts CpCo(CHR)(oxddt)] (R = H (3a), SiMe3 (3b)). Adduct 3a further reacted with protic acids (HX) to give some S-methylated adducts CpCo(X)(oxddt)(S-Me)] (X = Cl (4a), OCOCF3 (4c)), followed by the Co-C bond cleavage in the three-membered cobaltathiirane ring. Two different Z-shaped and U-shaped molecular structures were observed by X-ray diffraction studies. In the former structure (Z), the dithiolene and o-xylylene planes are located at almost parallel position each other, and in the latter structure (U), both planes are not parallel but the o-xylylene moiety is located closer to the dithiolene plane than the Z-shaped one. The Z-shaped structure involves 1 and 2. The U-shaped structure involves 3a, 3b, 4a and 4c. Complex 1 showed a one-dimensional chain through intermolecular π-π interaction in the crystal. Complex 2 had a dimeric interaction between dithioethylenedithiolate moieties (S2C2S2) in the oxddt. The SiMe3 group in 3b was placed at an exo-position with respect to the cobaltadithiolene ring due to a steric hindrance from the U-shaped oxddt ligand. In 4a, the X and Me groups are located at the opposite side of the dithiolene plane (anti-form) but in 4c, both groups are presented at the same side of the dithiolene plane (syn-form). The NMR analysis of 4a in solution indicated existence of both anti- and syn-isomers (7:1).
Keywords:Dithiolene  Oxddt  Alkylidene adduct  Molecular structure  Eight-membered ring
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