A DFT Protocol for the Prediction of 31P NMR Chemical Shifts of Phosphine Ligands in First-Row Transition-Metal Complexes,Organometallics

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A DFT Protocol for the Prediction of 31P NMR Chemical Shifts of Phosphine Ligands in First-Row Transition-Metal Complexes
Organometallics ( IF 2.5 ) Pub Date : 2020-08-25 , DOI: 10.1021/acs.organomet.0c00309
Pierre-Adrien Payard ₁ , Luca Alessandro Perego _{1,

2} , Laurence Grimaud ₁ , Ilaria Ciofini ₂

Affiliation

While ³¹P NMR is a major technique to characterize phosphine-ligated transition-metal complexes—which are ubiquitous in catalysis—³¹P NMR chemical shifts are difficult to predict using empirical rules or tabulated data. Aiming at filling this gap, we propose here guidelines enabling their prediction at a modest computational cost. Rooted in density functional theory, our protocol features structural optimization and magnetic shielding tensor calculations performed at a global hybrid level using a tailored locally dense basis set. Validation on an experimental data series revealed that while a careful conformational analysis is required in the case of flexible phosphines, the use of the free ligand or another complex as a reference for chemical shifts often allows solving this drawback. Applicability to various diamagnetic complexes of first-row transition metals is demonstrated, including large systems relevant to contemporary catalysis.

中文翻译：

DFT协议用于预测第一行过渡金属配合物中膦配体的³¹ P NMR化学位移

尽管³¹ P NMR是表征在催化作用中普遍存在的膦连接的过渡金属络合物的一项主要技术，但³¹使用经验法则或列表数据很难预测P NMR化学位移。为了填补这一空白，我们在此提出一些指导方针，以适度的计算成本实现其预测。根植于密度泛函理论，我们的协议具有结构优化和磁屏蔽张量计算的功能，该过程使用定制的局部密集基集在全局混合级别上执行。对一系列实验数据的验证表明，在使用柔性膦的情况下，需要进行仔细的构象分析，但使用游离配体或另一种配合物作为化学位移的参考通常可以解决这一问题。证明了其对第一行过渡金属的各种抗磁性配合物的适用性，包括与现代催化相关的大型系统。

更新日期：2020-09-14

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