冠醚环化二硫烯双核Au(Ⅰ)配合物的合成、结构及电化学性质

Syntheses,Structures and Electrochemical Properties of Dinuclear Au(Ⅰ) Complexes Including Crown Ether Annelated Dithiolate Ligands

合成了含有冠醚环化二硫烯的双核Au(Ⅰ)配合物[(3O-C2S4)Au2(PPh3)2](1),[(4O-C2S4)Au2.(PPh3)2](2),[(3O-C6S8)Au2(PPh3)2](3)和[(4O-C6S8)Au2(PPh3)2](4)以及富硫配合物[(btdt)Au2.(PPh3)2](5).通过X射线单晶衍射对配合物1～3和5进行了结构表征,并采用循环伏安法研究了配合物的氧化还原性质.研究结果表明,配合物4对Na+离子有明显的电化学响应,峰电位可以产生大约55 mV的正移动.

A series of new Au（Ⅰ） complexes containing crown ether annelated dithiolate ligands,[（3O-C2S4）Au2（PPh3）2]（1,3O-C2S4^2- =1,4,7-trioxa-10,13-dithiacyclopentadec-11-ene-11,12-dithiolate）,[（4O-C2S4）Au2（PPh3）2]（2,4O-C2S2-4=1,4,7,10-tetraoxa-13,16-dithiacyclooctadec-14-ene-14,15-dithiolate）,[（3O-C6S8）Au2（PPh3）2][3,3O-C6S8^2- =2-{4,5-dithia-（3′,6′,9′-trioxaundecyl）-1,3-dithiol-2-yli-dene}-1,3-dithiol-4,5-dithiolate],and [（4O-C6S8）Au2（PPh3）2][4,4O-C6S2-8=2-{4,5-dithia-（3′,6′,9′,12′-tetr-aoxatetradecyl）-1,3-dithiol-2-ylidene}-1,3-dithiol-4,5-dithiolate],and the sulphur-rich dithiolate Au（Ⅰ） complex [（btdt）Au2（PPh3）2]（5,btdt = benzotetrathiafulvalenedithiolate） were prepared and characterized.The crystal structures of complexes 1—3 and 5 were determined.Redox properties of these complexes were investigated by cyclic voltammetry and complex 4 shows significant response for Na＋ ions with a large positive shift of ca.55 mV.