Toluene and ethylbenzene aliphatic C-H bond oxidations initiated by a dicopper(II)-mu-1,2-peroxo complex.
Toluene and ethylbenzene aliphatic C-H bond oxidations initiated by a dicopper(II)-mu-1,2-peroxo complex.
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DOI：
10.1021/ja807081d
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发表时间：
2009-03-11
影响因子：
15
通讯作者：
Karlin KD
中科院分区：
文献类型：
--
作者：
Lucas HR;Li L;Sarjeant AA;Vance MA;Solomon EI;Karlin KD
单核化合物[CuI（OL）（MeCN）]B（C6 F5）4（OLCuI）与O2在非配位溶剂中于-80 °C下反应，生成μ-1，2-过氧双铜（II）配合物[{OLCuII}2（O22-）]2+。这种过氧复合物在甲苯或甲苯存在下的热衰变导致罕见的C-H活化化学;分别形成苯甲醛和苯乙酮/1-苯基乙醇混合物。用18 O2的实验证实产物中的氧源是分子O2，氘标记实验表明甲苯氧化的kH/kD = 7.5 ± 1。[CuI（BzL）（CH 3CN）]+（BzLCuI）的O2-反应在-80 °C下导致二铜（III）-双-μ-氧代物质[{BzLCuIII}2（μ-O2-）2]2+，并且从这样的溶液中，发生非常类似的甲苯氧化化学。配体BzL是三齿螯合物，具有与OL中相同的部分，但没有苯甲醚O-原子供体。在这些情况下，氧化剂物种的性质或衍生自[{OLCuII}2（O22-）]2+进行了讨论，并详细说明了甲苯H原子提取化学引发的反应可能的机制。为了确认双氧加合物的结构配方，已经进行了紫外-可见和共振拉曼光谱研究，并报告了这些结果，并将其与先前描述的包括[{CuII（PYL）}2（O2）]2+（PYL =TMPA =三（2-甲基吡啶基）胺）的系统进行了比较。使用（L）CuI，CO结合性质（即，νC-O值）沿着电化学性质比较，评估OL、BzL和PYL的相对给体能力。
With an anisole containing polypyridylamine potential tetradentate ligand OL, a μ-1,2-peroxo-dicopper(II) complex [{OLCuII}2(O22-)]2+ forms from the reaction of the mononuclear compound [CuI(OL)(MeCN)]B(C6F5)4(OLCuI) with O2 in non-coordinating solvents at -80 °C. Thermal decay of this peroxo complex in the presence of toluene or ethylbenzene leads to rarely seen C-H activation chemistry; benzaldehyde and acetophenone/1-phenylethanol mixtures, respectively, are formed. Experiments with 18O2 confirm that the oxygen source in the products is molecular O2 and deuterium labeling experiments indicate kH/kD = 7.5 ± 1 for the toluene oxygenation. The O2-reaction of [CuI(BzL)(CH3CN)]+ (BzLCuI) leads to a dicopper(III)-bis-μ-oxo species [{BzLCuIII}2(μ-O2-)2]2+ at -80 °C and from such solutions, very similar toluene oxygenation chemistry occurs. Ligand BzL is a tridentate chelate, possessing the same moiety found in OL, but without the anisole O-atom donor. In these contexts, the nature of the oxidant species in or derived from [{OLCuII}2(O22-)]2+ is discussed and likely mechanisms of reaction initiated by toluene H-atom abstraction chemistry are detailed. To confirm the structural formulations of the dioxygen-adducts, UV-vis and resonance Raman spectroscopic studies have been carried out and these results are reported and compared to previously described systems including [{CuII(PYL)}2(O2)]2+ (PYL =TMPA = tris(2-methylpyridyl)amine). Using (L)CuI, CO-binding properties (i.e., νC-O values) along with electrochemical property comparisons, the relative donor abilities of OL, BzL and PYL are assessed.
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