ИСТИНА

New substituted carborane deivatives were synthesized that were used as ligands for preparation of σ- and π- metallocomplexes. Nido-carborane thioethers Cs[X-(CH2)nSMe-7,8-C2B9H11)] (X=7, 9, n=0; X=9, n=0, 1) were synthesized and their reactions with tungsten carbonyl W(CO)5(THF) were investigated. The corresponding pentacarbonyl tungsten complexes were isolated as cesium salts and characterized [1]. Charge-compensated nido-carboranyl thioether ligands [7-MeS-10-Me2S-7,8-C2B9H10] and [7,8-(MeS)2-10-Me2S-7,8-C2B9H9] were prepared and fully characterized. They readily react with labile tungsten carbonyls to give σ-complexes – mono-substituted (CO)5W[7-MeS-10-Me2S-7,8-C2B9H10-κ1-S(1)], (CO)5W[7,8-(MeS)2-10-Me2S-7,8-C2B9H9-κ1-S(1)] and chelate (CO)4W[7,8-(MeS)2-10-Me2S-7,8-C2B9H9-κ2-S(1),S(2)]. The synthesized metallocomplexes were characterized by multinuclear NMR spectroscopy and single crystal X-ray diffraction [2]. A series of novel neutral nido-carboranes [9-Z(CH2)nMe2N-nido-7,8-C2B9H11] with various pendant functional groups was synthesized by copper(II) promoted reaction of the parent nido-carborane with dimethylalkylamines. In solution [9-HO(CH2)3Me2N-nido-7,8-C2B9H11] undergoes cyclization to give unusual [κO-4,κN-9-(μ-O(CH2)3Me2N)-nido-7,8-C2B9H10]. Several new carborane derivatives were synthesized, and dicarbollide ligands prepared from them were used for synthesis a series of novel bis(dicarbollide)metal compounds. Acknowledgements. Authors thanks coworkers mentioned in publications cited. This work was partially supported by the Russian Foundation for Basic Research (grant 13-03-00581). References. 1. S.V.Timofeev, M.V.Zakharova, E.M.Mosolova, I.A.Godovikov, I.V.Ananyev, I.B.Sivaev, V.I.Bregadze, J. Organomet. Chem., 2012, 721-722, 92-96. 2. S.V.Timofeev, O.B.Zhidkova, E.M.Mosolova, I.B.Sivaev, I.A.Godovikov, K.Yu.Suponitsky, Z.A.Starikova, V.I.Bregadze, Dalton Trans., 2015, 44, 6449-6456.