一种新型含[Mo2S4]2+单元的双核簇合物的合成.docVIP

  Synthesis of a New Dinuclear Cluster Containing [Mo2S4]2+ Core by Facile C–S Bond Formation ZHANG Wenhua, DAI Ming, LI Hongxi, REN Zhigang, LANG Jianping** 5 10 15 20 25 30 35 40 (College of Chemistry, Chemical Engineering and Materials Science, Soochow University, JiangSu SuZhou 215123) Abstract: Efforts in the construction of a new dinuclear cluster complex containing [Mo2S4]2+ core have been presented. Facile C–S bond formation reaction between the preformed cluster complex [Et4N]2[Mo2S4(edt)2] (edt = –SCH2CH2S–) (1) and benzylbromide in MeCN gave rise to a neutral bis-alkylated compound [Mo2S4(edtb)2] (edtb = –S(CH2Ph)CH2CH2S–) (2) in high yield. Compound 2 was characterized by elemental analysis, IR spectra, 1H NMR and single crystal X-ray crystallography. X-ray analysis demonstrated that the [Mo2S4] fragment in 1 is retained in 2, and the alkylation reaction took place at the two trans-aligned μ-S atoms of the two edt ligands. Keywords: C–S bond formation; [Mo2S4] core; molybdenum cluster; synthesis; crystal structure 0 Introduction Original interest in the cluster complexes containing [Mo2S4]2+ cores was motivated by the fact that these complexes were related to the structural and reactivity centers in many biological redox models as well as in industrially catalytic processes.1–10 In the past few years, we and others have been interested in the exploration of the reactivities of a dinuclear cluster compound [Et4N]2[Mo2S4(edt)2] (edt = –SCH2CH2S–) (1) due to its ‘sulfido-rich’ characteristic.11–15 A rich chemistry of 1, particularly its coordination chemistry towards a series coinage metal Cu(I), Ag(I) and Au(I) derivatives, has been revealed, as exemplified by the isolation of various types of high nuclear cluster aggregates, such as incomplete cubanes,11 cubanes,12–14 cages15 et al. On the other hand, the alkylation of the active sulfide centers using a wide range of alkyl halides provide facile means, instead of the usually tedious and cumbersome de