Expansion of the Ligand Knowledge Base for Monodentate P-Donor Ligands (LKB-P)

Abstract

We have expanded the ligand knowledge base for monodentate P-donor ligands (LKB-P, Chem. Eur. J. 2006, 12, 291-302) by 287 ligands and added descriptors derived from computational results on a gold complex [AuClL]. This expansion to 348 ligands captures known ligand space for this class of monodentate two-electron donor ligands well, and we have used principal component analysis (PCA) of the descriptors to derive an improved map of ligand space. Potential applications of this map, including the visualization of ligand similarities/differences and trends in experimental data, as well as the design of ligand test sets for high-throughput screening and the identification of ligands for reaction optimization, are discussed. Descriptors of ligand properties can also be used in regression models for the interpretation and prediction of available response data, and here we explore such models for both experimental and calculated data, highlighting the advantages of large training sets that sample ligand space well. † Development of a Ligand Knowledge Base, Part 6. See refs 1-5 for Parts 1-5.

CO2 Insertion into Metal–Carbon Bonds: A Computational Study of RhI Pincer Complexes

“…[19] For the present computational exploration, rhodium complexes were chosen for a number of reasons. Many rhodium complexes are active catalysts for C À C bond-forming reactions, [20] and Rh complexes were also described to react with CO 2.…”

Structure–Activity Relationship of Palladium Phosphanesulfonates: Toward Highly Active Palladium‐Based Polymerization Catalysts

“…Values of the descriptors of each ligand can be found in references [21] and [22]. Lutidine complexes: c, d, f, g, and h, pyridine complexes: a, b, i; no base: e. Table 3.…”

“…Thus we have correlated our activity data with phosphane descriptors listed in the ligand knowledge base for monodentate P donors (LKB-P). [21] We have compared each of our bidentate ligands with the corresponding trialkyl or triarylphosphane: for example, for ligand 1 e, descriptor values of PA C H T U N G T R E N N U N G (C 6 F 5 ) 3 were used. The LKB-P lists 348 P-ligands for which 26 descriptors are reported.…”

“…The He 8 steric descriptor is the interaction energy between the ligand in its groundstate conformation and a ring cluster of 8 He atoms. It has been shown to correlate well with the Tolman cone angle, [21] and it is an acceptable descriptor to assess the influence of steric factors. The BE(B) descriptor describes the bond energy between BH 3 and the ligand (in kcal mol À1 ).…”

The Application of Advanced Design of Experiments for the Efficient Development of Chemical Processes

“…PCA solvent maps have been developed and used for chemical reactions and polymorph screening [7][8][9][10]. PCA has also been used successfully for ligand mapping by us in collaboration with the University of Bristol [11][12] as well as for amines, aldehydes, ketones and Lewis acids [13][14][15].…”