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首页> 外文期刊>Chemistry: A European journal >Establishing the Coordination Chemistry of Antimony(V) Cations: Systematic Assessment of Ph4Sb(OTf) and Ph3Sb(OTf)(2) as Lewis Acceptors
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Establishing the Coordination Chemistry of Antimony(V) Cations: Systematic Assessment of Ph4Sb(OTf) and Ph3Sb(OTf)(2) as Lewis Acceptors

机译：建立锑（V）阳离子的配位化学：系统评估Ph4Sb（OTf）和Ph3Sb（OTf）（2）作为路易斯受体

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摘要

The coordination chemistry of the stiboranes Ph4Sb(OTf) (1a, OTf = OSO2CF3) and Ph3Sb(OTf)(2) (3) with Lewis bases has been investigated. The significant steric encumbrance of the Sb center in 1a precludes interaction with most ligands, but the relatively low steric demands of 4-methylpyridine-N-oxide (OPyrMe) and OPMe3 enabled the characterization of [Ph4Sb(OPyrMe)][OTf] (2a) and [Ph4Sb(OPMe3)][OTf] (2b), rare examples of structurally characterized complexes of stibonium acceptors. In contrast, 3 was found to engage a variety of Lewis bases, forming stable isolable complexes of the form [Ph3Sb(donor)(2)][OTf](2) [donor=OPMe3 (6a), OPCy3 (6b, Cy=cyclohexyl), OPPh3 (6c), OPyrMe (6d)], [Ph3Sb(dmap)(2)(OTf)][OTf] (6e, dmap=4-(dimethylamino)pyridine) and [Ph3Sb(donor)(OTf)][OTf] [donor=1,10-phenanthroline (7a) or 2,2-bipy (7b, bipy=bipyridine)]. These compounds exhibit significant structural diversity in the solid-state, and undergo ligand exchange reactions in line with their assignment as coordination complexes. Compound 3 did not form stable complexes with phosphine donors, with reactions instead leading to redox processes yielding SbPh3 and products of phosphine oxidation.
机译：研究了带有路易斯碱的西硼烷Ph4Sb（OTf）（1a，OTf = OSO2CF3）和Ph3Sb（OTf）（2）（3）的配位化学。 Sb中心在1a中存在显着的空间阻碍，无法与大多数配体相互作用，但是4-甲基吡啶-N-氧化物（OPyrMe）和OPMe3相对较低的空间需求使得[Ph4Sb（OPyrMe）] [OTf]的表征成为可能。 ）和[Ph4Sb（OPMe3）] [OTf]（2b），这是sti受体的结构特征复杂的稀有例子。相反，发现3可以与多种Lewis碱基结合，形成[Ph3Sb（donor）（2）] [OTf]（2）形式的稳定的可分离复合物[donor = OPMe3（6a），OPCy3（6b，Cy =环己基），OPPh3（6c），OPyrMe（6d）]，[Ph3Sb（dmap）（2）（OTf）] [OTf]（6e，dmap = 4-（二甲基氨基）吡啶）和[Ph3Sb（供体）（OTf） ] [OTf] [供体＝ 1，10-菲咯啉（7a）或2，2-联吡啶（7b，联吡啶＝联吡啶）]。这些化合物在固态中表现出显着的结构多样性，并根据其作为配位络合物的分配进行配体交换反应。化合物3没有与膦供体形成稳定的配合物，而是反应导致氧化还原过程，生成SbPh3和膦氧化产物。

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