三-2-吡啶基膦配体的配位和给体性质的实验与理论研究

An experimental and theoretical study of the coordination and donor properties of tris-2-pyridyl-phosphine ligands.

作者信息

Hanf Schirin, Colebatch Annie L, Stehr Philipp, García-Rodríguez Raúl, Hey-Hawkins Evamarie, Wright Dominic S

机构信息

Chemistry Department, University of Cambridge, Lensfield Road, CB2 1EW, Cambridge, UK.

Institute of Inorganic Chemistry, Faculty of Chemistry and Mineralogy, Leipzig University, Johannisallee 29, 04103 Leipzig, Germany.

出版信息

Dalton Trans. 2020 Apr 28;49(16):5312-5322. doi: 10.1039/d0dt00609b.

DOI:10.1039/d0dt00609b

PMID:32242884

Abstract

The coordination characteristics and donor/acceptor properties of a series of 2-pyridyl substituted phosphine ligands have been investigated using structural, spectroscopic and DFT calculational studies. A range of different coordination modes are observed in Mo and W carbonyl complexes of tris-2-pyridyl-phosphine ligands of the type P(2-py') (2-py' = substituted or unsubstituted 2-pyridyl group), including an unprecedented example exhibiting N,N',μ2-π coordination. DFT calculations were used to assess the relative donor/acceptor properties of a range of related 2-pyridyl-phosphine ligands with respect to PPh3 and PtBu3.

摘要

通过结构、光谱和密度泛函理论（DFT）计算研究，对一系列2-吡啶基取代的膦配体的配位特征以及给体/受体性质进行了研究。在P(2-py')型三-2-吡啶基膦配体（2-py' = 取代或未取代的2-吡啶基）的钼和钨羰基配合物中观察到了一系列不同的配位模式，包括一个呈现N,N',μ2-π配位的前所未有的例子。利用DFT计算评估了一系列相关2-吡啶基膦配体相对于三苯基膦（PPh3）和三叔丁基膦（PtBu3）的相对给体/受体性质。