Reactions of diphenyltellurium oxide with organostibonic acid and polymeric triphenylantimony oxide have been investigated independently. Single crystal X-ray diffraction studies have revealed the formation of novel and rare mixedvalent Sb(V)/(III) containing polyoxostibonates (C6H5)3Te}2Na2(H2O)2(p-Br-C6H4SbV)10(SbIII)4[(C6H5)2Te]4(O)30(OH)4} 1 and (C6H5)3Te}4[(C6H5)2SbV]4(SbIII)4(O)12(OH)4}
已经独立研究了二苯基氧化碲与有机二磺酸和聚合的三苯基氧化锑的反应。单晶X射线衍射研究表明,新型和稀有的混合价Sb(V)/(III)的形成包含多氧西ib苯磺酸盐(C 6 H 5)3 Te} 2 Na 2(H 2 O)2(p- Br-C 6 H 4 Sb V)10(Sb III)4 [(C 6 H 5)2 Te] 4(O)30(OH) 4 } 1和(C 6 H 5) 3 Te} 4 [(C 6 H 5) 2 Sb V ] 4(Sb III) 4(O) 12(OH) 4 } 2。溶液125 Te NMR支持所示的固态结构。有趣的是,在这些POM的组装过程中,几个过程同时发生。很少观察到从Sb( V)还原为Sb( III)),有机锑前体的完全脱芳基化和稳定大而新颖的POM结构(如1所示)的四有机二碲氧烷部分的络合能力以及三苯基碲阳离子的形成,不仅可提供电荷平衡,而且还可稳定POM构架(如2所示)弱相互作用的报道。
Tetranuclear stiboxanes (RSb)4O6, exhibiting an adamantane-type structure
作者:Ananda Kumar Jami、Viswanathan Baskar
DOI:10.1039/c2dt30587a
日期:——
Depolymerization reactions of organostibonic acids with protic ligands have been investigated. Reaction of arylstibonic acids with 8-hydroxyquinoline (8-HQ), or 2-[1H-pyrazol-5(3)-yl]naphthalene-1-ol} (H2naphpz) in a 1 : 1 stoichiometry in refluxing toluene affords adamantane-like L4(RSb)4O6 clusters [(p-XC6H4Sb)4(O)6(Q)4] (where X = Cl (1), Br (2), QH = 8-hydroxyquinoline), [(p-ClC6H4Sb)4(O)6(Hnaphpz)4]·H2naphpz (3) and [(p-Br-C6H4Sb)4(O)6(Hnaphpz)4]2·H2naphpz (4). Further a tetrameric organoantimony oxo cluster, L4(RSb)4O4 [(p-ClC6H4Sb)4(O)4(naphpz)4] (5) has also been isolated as a side product in the reaction of arylstibonic acid with naphthylphenolic pyrazole. Interestingly 1–4 structurally resemble the dimeric form of the antimony oxide Sb2O3 and its mineral senarmontite.
The reaction of RSbO3H2 with t-butylsilanetriol has led to the isolation of organoantimony(v) based molecular triangles stabilized by siloxane frameworks.