Shaobin Miao

A disulfide-bridged manganese carbonyl anion: synthesis, structure and reactivity of [Mn3(CO)10(μ3-S2)2]−

Abstract The reduction of Mn2(CO)7(μ-S2), (1) with sodium amalgam in THF provided the new monoanion [Mn3(CO)10(μ3-S2)2]−, (3) isolated in low yield as the [Ph3PMe] salt. The reaction of Mn4(CO)15(μ3-S2)(μ4-S2), (2) with [Ph3PMe]I provided the same salt [Ph3PMe] [3] in a good yield, 68%. Anion 3 reacts [CpFe(CO)2(acetone)]BF4 to yield the neutral mixed metal complex CpFeMn3(CO)12(μ3-S2)(μ4-S2), (4). The structures of [Ph3PMe] [3] and 4 were determined by single crystal X-ray diffraction analyses. The core of the structure of 3 consists of two [Mn(CO)3] groups bridged by two disulfido ligands in a μ2–η2 fashion with an additional [Mn(CO)4] group that bridges the two disulfido ligands. The CpFe(CO)2 group in 4 is bonded to a sulfur atom of one of the two disulfido ligands of the anionic grouping of 3.

Synthesis and properties of tetracyanoquinodimethane derivatives

Abstract Two new aza-acenequinone derivatives 4 and 5 were prepared by cyclocondensation of diamines 2 and 3 with bis(triisopropylsilyl)-dialkynyl-l,2-dione 1. Further reactions of compounds 4 and 5 with malononitrile using the Lehnert reagent afforded corresponding tetracyanoquinodimethane (TCNQ) derivatives 6 and 7. Compounds 4, 6 and 7 were characterized by single crystal X-ray diffraction techniques. Compounds 6 and 7 were studied electrochemically and photochemically. Density functional theory (DFT) calculations on compounds 6 and 7 indicate that both compounds have the potential to be candidates for organic semiconductor materials.