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The hydrogen bond, front and center.氢键，处于核心位置。
Angew Chem Int Ed Engl. 2010 Dec 27;49(52):10045-7. doi: 10.1002/anie.201002928.
2
Recent advancements and challenges of palladium(II)-catalyzed oxidation reactions with molecular oxygen as the sole oxidant.以分子氧作为唯一氧化剂的钯（II）催化氧化反应的最新进展与挑战
Chem Commun (Camb). 2009 Jul 14(26):3854-67. doi: 10.1039/b902868d. Epub 2009 May 14.
3
Mechanism of Pd(OAc)2/pyridine catalyst reoxidation by O2: influence of labile monodentate ligands and identification of a biomimetic mechanism for O2 activation.氧气对醋酸钯/吡啶催化剂的再氧化机理：不稳定单齿配体的影响及氧气活化仿生机理的确定
Chemistry. 2009;15(12):2915-22. doi: 10.1002/chem.200802311.
4
Mechanism for activation of molecular oxygen by cis- and trans-(pyridine)2Pd(OAc)H: Pd(0) versus direct insertion.顺式和反式-(吡啶)₂Pd(OAc)H 活化分子氧的机制：Pd(0) 与直接插入
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Reaction of molecular oxygen with a Pd(II)-hydride to produce a Pd(II)-hydroperoxide: experimental evidence for an HX-reductive-elimination pathway.分子氧与钯（II）-氢化物反应生成钯（II）-氢过氧化物：HX还原消除途径的实验证据。
J Am Chem Soc. 2008 Apr 30;130(17):5753-62. doi: 10.1021/ja7112504. Epub 2008 Apr 5.
6
Pd-mediated activation of molecular oxygen: Pd(0) versus direct insertion.
J Am Chem Soc. 2007 Aug 29;129(34):10361-9. doi: 10.1021/ja070462d. Epub 2007 Aug 3.
7
Insertion of molecular oxygen into a palladium-hydride bond: computational evidence for two nearly isoenergetic pathways.分子氧插入钯-氢键：两条近等能途径的计算证据。
J Am Chem Soc. 2007 Apr 11;129(14):4410-22. doi: 10.1021/ja069037v. Epub 2007 Mar 20.
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Mechanism of direct molecular oxygen insertion in a palladium(II)-hydride bond.
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The performance of hybrid DFT for mechanisms involving transition metal complexes in enzymes.杂化密度泛函理论在涉及酶中过渡金属配合物的反应机理方面的性能。
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Reaction of molecular oxygen with a PdII- hydride to produce a PdII-hydroperoxide: acid catalysis and implications for Pd-catalyzed aerobic oxidation reactions.
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O2 与 [(-)-sparteine]Pd(H)Cl 的反应：支持分子内 [H-L]+“还原消除”途径的证据。

Reaction of O2 with [(-)-sparteine]Pd(H)Cl: evidence for an intramolecular [H-L]+ "reductive elimination" pathway.

机构信息

Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States.

出版信息

J Am Chem Soc. 2011 Aug 31;133(34):13268-71. doi: 10.1021/ja204989p. Epub 2011 Aug 4.

DOI:10.1021/ja204989p
PMID:21790197
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC3161160/
Abstract

(Sp)PdCl(2) [Sp = (-)-sparteine] catalyzes a number of different aerobic oxidation reactions, and reaction of O(2) with a Pd(II)-hydride intermediate, (Sp)Pd(H)Cl (1), is a key step in the proposed catalytic mechanism. Previous computational studies suggest that O(2) inserts into the Pd(II)-H bond, initiated by abstraction of the hydrogen atom by O(2). Experimental and computational results obtained in the present study challenge this conclusion. Oxygenation of in-situ-generated (Sp)Pd(H)Cl exhibits a zero-order dependence on [O(2)]. This result is inconsistent with a bimolecular H-atom-abstraction pathway, and DFT computational studies identify a novel "reductive elimination" mechanism, in which the chelating nitrogen ligand undergoes intramolecular deprotonation of the Pd(II)-hydride. The relevance of this mechanism to other Pd(II) oxidation catalysts with chelating nitrogen ligands is evaluated.

摘要

(Sp)PdCl(2)[Sp=(-)-sparteine]催化许多不同的有氧氧化反应，而 O(2)与 Pd(II)-氢化物中间体(Sp)Pd(H)Cl(1)的反应是所提出的催化机理中的关键步骤。先前的计算研究表明，O(2)通过 O(2)夺取氢原子而插入 Pd(II)-H 键。本研究中获得的实验和计算结果对这一结论提出了挑战。原位生成的(Sp)Pd(H)Cl 的氧化对[O(2)]表现出零级依赖性。这一结果与双分子 H 原子攫取途径不一致，并且 DFT 计算研究确定了一种新的“还原消除”机制，其中螯合氮配体经历 Pd(II)-氢化物的分子内去质子化。评估了该机理对具有螯合氮配体的其他 Pd(II)氧化催化剂的相关性。