Stauber Julia M, Müller Peter, Dai Yizhe, Wu Gang, Nocera Daniel G, Cummins Christopher C
Department of Chemistry , Massachusetts Institute of Technology , 77 Massachusetts Avenue , Cambridge , MA 02139-4307 , USA . Email:
Department of Chemistry , Queen's University , 90 Bader Lane , Kingston , Ontario , Canada K7L 3N6 . Email:
Chem Sci. 2016 Dec 1;7(12):6928-6933. doi: 10.1039/c6sc01754a. Epub 2016 Jul 6.
Cofacial bimetallic tin(ii) ([Sn(BDCA-5t)], ) and lead(ii) ([Pb(BDCA-5t)], ) complexes have been prepared by hexadeprotonation of hexacarboxamide cryptand BDCA-5t-H together with double Sn(ii) or Pb(ii) insertion. Reaction of with elemental sulfur or selenium generates di-tin polychalcogenide complexes containing μ-E and bridging μ-E ligands where E = S or Se, and the Sn(ii) centers have both been oxidized to Sn(iv). Solution and solid-state UV-Vis spectra of [(μ-S)Sn(μ-S)(BDCA-5t)] () indicate that the complex acts reversibly as a source of S˙ in DMF solution with a = 0.012 ± 0.002. Reductive removal of all six chalcogen atoms is achieved through treatment of [(μ-E)Sn(μ-E)(BDCA-5t)] with PR (R = Bu, Ph, OPr) to produce six equiv. of the corresponding EPR compound with regeneration of di-tin(ii) cryptand complex .
通过六羧酰胺穴状配体BDCA - 5t - H的六去质子化以及双Sn(ii)或Pb(ii)插入反应，制备了共面双金属锡(ii)（[Sn(BDCA - 5t)]）和铅(ii)（[Pb(BDCA - 5t)]）配合物。[Sn(BDCA - 5t)]与元素硫或硒反应生成含有μ - E和桥连μ - E配体的二锡多硫属化物配合物，其中E = S或Se，且Sn(ii)中心均被氧化为Sn(iv)。[(μ - S)Sn(μ - S)(BDCA - 5t)]（）的溶液和固态紫外 - 可见光谱表明，该配合物在DMF溶液中可逆地作为S˙源，其 = 0.012 ± 0.002。通过用PR（R = Bu、Ph、OPr）处理[(μ - E)Sn(μ - E)(BDCA - 5t)]，实现了所有六个硫属原子的还原去除，生成六个当量的相应EPR化合物，并再生二锡(ii)穴状配体配合物。
