Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg , 4 Rue Blaise Pascal, CS 90032, 67081 Strasbourg, France.
Laboratoire de Chimie de Coordination (LCC), CNRS-UPR 8241, 205 Route de Narbonne, Toulouse F-31077 Cedex 4, France.
Chem Rev. 2016 Aug 24;116(16):9237-304. doi: 10.1021/acs.chemrev.6b00153. Epub 2016 Jul 26.
The aim of this review is to highlight how the diversity generated by N-substitution in the well-known short-bite ligand bis(diphenylphosphino)amine (DPPA) allows a fine-tuning of the ligand properties and offers a considerable scope for tailoring the properties and applications of their corresponding metal complexes. The various N-substituents include nitrogen-, oxygen-, phosphorus-, sulfur-, halogen-, and silicon-based functionalities and directly N-bound metals. Multiple DPPA-type ligands linked through an organic spacer and N-functionalized DRPA-type ligands, in which the PPh2 substituents are replaced by PR2 (R = alkyl, benzyl) groups, are also discussed. Owing to the considerable diversity of N-functionalized DPPA-type ligands available, the applications of their mono- and polynuclear metal complexes are very diverse and range from homogeneous catalysis with well-defined or in situ generated (pre)catalysts to heterogeneous catalysis and materials science. In particular, sustained interest for DPPA-type ligands has been motivated, at least in part, by their ability to promote selective ethylene tri- or tetramerization in combination with chromium. Ligands and metal complexes where the N-substituent is a pure hydrocarbon group (as opposed to N-functionalization) are outside the scope of this review. However, when possible, a comparison between the catalytic performances of N-functionalized systems with those of their N-substituted analogs will be provided.
本文旨在强调通过在著名的短位配体双（二苯基膦基）胺（DPPA）中的 N 取代基的多样性，可以对配体性质进行微调，并为其相应金属配合物的性质和应用提供了很大的调整空间。各种 N 取代基包括氮、氧、磷、硫、卤素和硅基官能团以及直接与 N 键合的金属。通过有机间隔基连接的多个 DPPA 型配体和 N 官能化的 DRPA 型配体，其中 PPh2 取代基被 PR2（R = 烷基、苄基）取代基取代，也进行了讨论。由于可用的 N 官能化 DPPA 型配体具有相当大的多样性，其单核和多核金属配合物的应用非常多样化，范围从具有明确或原位生成（预）催化剂的均相催化到多相催化和材料科学。特别是，DPPA 型配体至少部分因其与铬结合促进选择性乙烯三聚或四聚的能力而引起了持续的兴趣。本文的范围不包括 N 取代基为纯烃基团（而非 N 官能化）的配体和金属配合物。然而，在可能的情况下，将提供 N 官能化系统与它们的 N 取代类似物的催化性能之间的比较。
