Routes to Heterotrinuclear Metal Siloxide Complexes for Cooperative Activation of O2.
Routes to Heterotrinuclear Metal Siloxide Complexes for Cooperative Activation of O2.
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异三核金属硅氧化物配合物协同活化 O2 的途径
DOI：
10.1021/acs.inorgchem.0c00279
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发表时间：
2020
影响因子：
4.6
通讯作者：
C. Limberg
中科院分区：
文献类型：
--
作者：
M.- L. Wind;S. Hoof;B. Braun-Cula;C. Herwig;C. Limberg
组装能够激活二氧的异金属配合物在合成上具有挑战性。本文报道了两种不同的方法制备杂金属超氧化物配合物[PhL2CrII -η - o2][MX]2(PhL = - oph2siosiph2o -, MX+= [CoCl]+, [ZnBr]+, [ZnCl]+)，从crii前体配合物[PhL2CrII]Li2(THF)4开始。第一种方法是在与双氧反应前，通过将mx2加入[PhL2CrII]Li2(THF)4，通过[MX]+交换Li+，而第二种方法是在o2活化后，通过将mx2加入[PhL2CrIII- 2o1 - o2]Li2(THF)4，进行盐的转化反应。第一种策略不适用于氧化还原活性金属离子，如Fe2+或Co2+，因为它会导致中心铬离子氧化，如[PhL2CrIIICl][CoCl]2(THF)3的分离。然而，它提供了杂双金属配合物[PhL2CrIII-η - o2][MX]2（[MX]+= [ZnBr]+, [ZnCl]+）与氧化还原活性的侧面金属结合。第二种策略不仅适用于氧化还原活性金属离子，也适用于氧化还原活性金属离子，并导致形成铬（III）超氧化物配合物[PhL2CrIII-η1-O2][MX]2（MX+= [ZnCl]+, [ZnBr]+, [CoCl]+）。稳定性和反应性研究的结果（采用TEMPO-H和苯酚作为底物）以及与碱金属系列（M+= Li+, Na+, K+）的比较证实，尽管稳定性取决于反离子M的刘易斯酸度和与之配合的溶剂分子的数量，但反应性强烈依赖于超氧化物部分的可及性。因此，在超氧化物中，用XZn+取代Li+可以得到更稳定的配合物，同时对O-H基团的反应性更强。因此，本文提出的方法拓宽了可获得的异金属o2活化化合物的范围，并为进一步调整[RL2CrIII-η - o2] m2配合物的反应性提供了基础。
The assembly of heterometallic complexes capable of activating dioxygen is synthetically challenging. Here, we report two different approaches for the preparation of heterometallic superoxide complexes [PhL2CrIII-η1-O2][MX]2(PhL =–OPh2SiOSiPh2O–, MX+= [CoCl]+, [ZnBr]+, [ZnCl]+) starting from the CrIIprecursor complex [PhL2CrII]Li2(THF)4. The first strategy proceeds via the exchange of Li+by [MX]+through the addition of MX2to [PhL2CrII]Li2(THF)4before the reaction with dioxygen, whereas in the second approach a salt metathesis reaction is undertaken after O2activation by adding MX2to [PhL2CrIII-η1-O2]Li2(THF)4. The first strategy is not applicable in the case of redox-active metal ions, such as Fe2+or Co2+, as it leads to the oxidation of the central chromium ion, as exemplified with the isolation of [PhL2CrIIICl][CoCl]2(THF)3. However, it provided access to the hetero-bimetallic complexes [PhL2CrIII-η1-O2][MX]2([MX]+= [ZnBr]+, [ZnCl]+) with redox-inactive flanking metals incorporated. The second strategy can be applied not only for redox-inactive but also for redox-active metal ions and led to the formation of chromium(III) superoxide complexes [PhL2CrIII-η1-O2][MX]2(MX+= [ZnCl]+, [ZnBr]+, [CoCl]+). The results of stability and reactivity studies (employing TEMPO–H and phenols as substrates) as well as a comparison with the alkali metal series (M+= Li+, Na+, K+) confirmed that although the stability is dependent on the Lewis acidity of the counterions M and the number of solvent molecules coordinated to those, the reactivity is strongly dependent on the accessibility of the superoxide moiety. Consequently, replacement of Li+by XZn+in the superoxides leads to more stable complexes, which at the same time behave more reactive toward O–H groups. Hence, the approaches presented here broaden the scope of accessible heterometallic O2activating compounds and provide the basis for further tuning of the reactivity of [RL2CrIII-η1-O2]M2complexes.
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通过铬 (II) 和锂阳离子之间 O2 活化形成的异双金属超氧化物复合物
影响因子：
--
作者：
F. Schax;S. Suhr;B. Braun;E. Bill;C. Herwig;C. Limberg
通讯作者：
C. Limberg
影响因子：
2.9
作者：
J. Vrettos;Daniel A. Stone;G. Brudvig
通讯作者：
J. Vrettos;Daniel A. Stone;G. Brudvig
硅氧化物二锂铜Cu(μ-OSiPh2OSiPh2O)2 [Li(THF)2]2的合成及X射线晶体结构
DOI：
--
发表时间：
1999
期刊：
影响因子：
--
作者：
W. Evans;Randy N. R. Broomhall;Dexter Simon;J. Ziller
通讯作者：
J. Ziller
影响因子：
--
作者：
M. Wind;S. Hoof;C. Herwig;B. Braun‐Cula;C. Limberg
通讯作者：
M. Wind;S. Hoof;C. Herwig;B. Braun‐Cula;C. Limberg
影响因子：
15
作者：
M. Wind;S. Hoof;B. Braun‐Cula;C. Herwig;C. Limberg
通讯作者：
M. Wind;S. Hoof;B. Braun‐Cula;C. Herwig;C. Limberg