Bonding Energetics of Palladium-amido/aryloxide Complexes in DMSO: Implications for Pd-mediated Aniline Activation.,Angewandte Chemie International Edition

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Bonding Energetics of Palladium-amido/aryloxide Complexes in DMSO: Implications for Pd-mediated Aniline Activation.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-09-10 , DOI: 10.1002/anie.202011313
Jun-Yan Wu ₁ , Zhen Li ₁ , Jin-Dong Yang ₁ , Jin-Pei Cheng _{1,

2}

Affiliation

Thermodynamic knowledge of the metal–ligand (M−L) σ‐bond strength is crucial to understanding metal‐mediated transformations. Here, we developed a method for determining the Pd−X (X=OR and NHAr) bond heterolysis energies (ΔG_het(Pd−X)) in DMSO taking [(tmeda)PdArX] (tmeda=N,N,N′,N′‐tetramethylethylenediamine) as the model complexes. The ΔG_het(Pd−X) scales span a range of 2.6–9.0 kcal mol⁻¹ for ΔG_het(Pd−O) values and of 14.5–19.5 kcal mol⁻¹ for ΔG_het(Pd−N) values, respectively, implying a facile heterolytic detachment of the Pd ligands. Structure‐reactivity analyses of a modeling Pd‐mediated X−H bond activation reveal that the M−X bond metathesis is dominated by differences of the X−H and Pd−X bond strengths, the former being more influential. The ΔG_het(Pd−X) and pK_a(X−H) parameters enable regulation of reaction thermodynamics and chemoselectivity and diagnosing the probability of aniline activation with Pd−X complexes.

中文翻译：

在DMSO中钯-酰胺基/芳基氧化物络合物的键能：对Pd介导的苯胺活化的影响。

金属-配体（ML）σ-键强度的热力学知识对于理解金属介导的转变至关重要。在这里，我们[[tmeda] PdArX]（tmeda = N，N，N ' ）提出了一种确定DMSO中Pd-X（X = OR和NHAr）键杂合能（ΔG _het（Pd-X））的方法。，N'-四甲基乙二胺）作为模型络合物。该Δ ģ _HET（PD-X）秤跨越范围2.6-9.0千卡摩尔^-1为Δ G ^ _HET（PD-O）的值和14.5-19.5千卡摩尔^-1为Δ G ^ _HET（Pd-N）值分别表示Pd配体的容易杂化分离。建模的Pd介导的X-H键活化的结构反应性分析表明，MX键的复分解作用主要受X-H和Pd-X键强度的差异影响，前者的影响更大。该Δ ģ _HET（PD-X）和p ķ_一个（X-H）参数使反应热力学和化学选择性的调节和诊断苯胺活化用Pd-X配合物的概率。

更新日期：2020-09-10

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