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首页> 外文期刊>Chemistry: A European journal >First dinuclear copper/gallium complexes: Supporting Cu~0and Cu~I centres by low-valent organogallium ligands
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First dinuclear copper/gallium complexes: Supporting Cu~0and Cu~I centres by low-valent organogallium ligands

机译：首个双核铜/镓络合物：通过低价有机镓配体支持Cu〜0和Cu〜I中心

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摘要

The synthesis and structural characterisation of low-valent dinuclear copper(I) and copper(0) complexes supported by organogallium ligands has been accomplished for the first time by the reductive coordination reaction of [GaCp~*] (Cp~* = pentamethylcyclopentadienyl) and [Ga(ddp)] (ddp = HC(CMeNC_6H_3-2,6-iPr_2:)_2 _2-diisopropylphenylamino-4-diisopropylphenylimino-2-pentene) with readily available copper(II) and copper(I) precursors. The treatment of CuBr_2 and Cu(OTf)_2 (OTf=CF_3SO_3) with [Ga(ddp)] under mild conditions resulted in elimination of [Ga(L)_2(ddp)] (L = Br, OTf) and afforded the novel gallium(I)/copper(I) compounds [{(ddp)GaCu(L)} _2] (L = Br (1), OTf (2)). The single-crystal X-ray structure determinations of 1 and 2 reveal that these molecules are composed of {(ddp)GaCu(L)} dimeric units, with planar Cu~1-Ga~1 four-membered rings and short Cu~I Cu~I distances, with 2 exhibiting the shortest Cu~I Cu~I contact reported to date of 2277(3) ?. The allgallium coordinated dinuclear [Cu_2 (GaCp~*)(μ-GaCp~*)_3Ga(OTf)_3] (3) is formed when Cu(OTf)_2 is combined with [GaCp~*] instead of [Ga(ddp)]. Notably, in the course of this redox reaction Lewis acidic Ga(OTf)3_ is formed, which coordinates to one of the electron-rich copper(0) centres. Compound 3 is suggested as the first case of a structurally characterised complex of copper(I). By changing the copper(II) to a copper(I) source, that is, [Cu(cod)_2][OTf] (cod=1,5-cyclooctadiene), the salt [Cu _2(GaCp~*)_3(μGaCp~*)_2][OTf] _2 (4) is formed, the cationic part of which is related to previously described isoelectronic dinuclear d~(10) complexes of the type [M _2(GaCp~*)_5] (M = Pd, Pt).
机译：有机镓配体负载的低价双核铜（I）和铜（0）配合物的合成和结构表征是通过[GaCp〜*]（Cp〜* =五甲基环戊二烯基）和[Ga（ddp）]（ddp = HC（CMeNC_6H_3-2,6-iPr_2：）_ 2 _2-二异丙基苯基氨基-4-二异丙基苯基亚氨基-2-戊烯），具有易于获得的铜（II）和铜（I）前体。在温和的条件下用[Ga（ddp）]处理CuBr_2和Cu（OTf）_2（OTf = CF_3SO_3）导致消除[Ga（L）_2（ddp）]（L = Br，OTf），并提供了新的镓（I）/铜（I）化合物[{（ddp）GaCu（L）} _2]（L = Br（1），OTf（2））。对1和2的单晶X射线结构测定表明，这些分子由{（ddp）GaCu（L）}二聚体单元组成，具有平面Cu〜1-Ga〜1四元环和短Cu〜I Cu〜I距离，其中2个展示了最短的Cu〜I Cu〜I接触，据报道为2277（3）？。当Cu（OTf）_2与[GaCp〜*]代替[Ga（ddp）]结合时，形成了镓配位双核[Cu_2（GaCp〜*）（μ-GaCp〜*）_ 3Ga（OTf）_3]（3）。 ]。明显地，在该氧化还原反应的过程中，形成路易斯酸的Ga（OTf）3_，其与富电子的铜（0）中心之一配位。建议将化合物3作为结构特征化的铜（I）配合物的第一种情况。通过将铜（II）更改为铜（I）源，即[Cu（cod）_2] [OTf]（cod = 1,5-环辛二烯），得到盐[Cu _2（GaCp〜*）_ 3（形成了μGaCp〜*）_ 2] [OTf] _2（4），其阳离子部分与先前描述的[M _2（GaCp〜*）_ 5]型等电子双核d〜（10）配合物有关（M = Pd，Pt）。

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