Synthesis of crown ethers with the incorporated cobalt bis(dicarbollide) fragment

A series of podands (acyclic analogues of crown ethers) related to 18-crown-6 was obtained by ring-opening reactions of the 1,4-dioxane derivative of nido-carborane [10-O(CH2CH2)(2)O-7,8-C2B9H11] with 1,2-S,S'- and O,O'-dinucleophiles (1,2-dimercaptoethane, 1,2-dimercaptobenzene, 1,2-dimercapto-ortho-carborane, 1,2-dihydroxy-ortho-carborane). By stepwise ring-opening reactions of the dioxane derivative with sulfur-containing nucleophiles the podand related to 15-crown-5 was prepared as well. The reactions of the obtained podands with CoCl2 result in the macrocyclic ring closure giving the corresponding crown ethers with the incorporated cobalt bis(dicarbollide) fragment K[8,8'-mu-S(OCH2CH2OCH2CH2)(2)-3,3'-Co(1,2-C2B9H9)(2)] and K[8,8'-mu-C6H4(OCH2CH2OCH2CH2S)(2)-3,3'-Co(1,2-C2B9H9)(2)]. The structure of Na [8,8'-mu-o-C6H4(OCH2CH2OCH2CH2S)(2)-3,3'-Co(1,2-C2B9H9)(2)] was determined by single crystal X-ray diffraction. (C) 2015 Elsevier BY. All rights reserved.