Evaluation of Pd→B Interactions in Diphosphinoborane Complexes and Impact on Inner‐Sphere Reductive Elimination. Issue 59 (18th September 2020)

• Record Type: Journal Article
• Authors: Ritter, Florian; John, Lukas; Schindler, Tobias; Schroers, Julian P.; Teeuwen, Simon; Tauchert, Michael E.
• Is Part Of: Chemistry. Volume 26:Issue 59(2020)
• Page Start: 13436
• Page End: 13444
• Publication Date: 2020-09-18
• Subjects: boranes -- donor–acceptor systems -- palladium -- phosphine ligands -- reductive elimination; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202001189
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The dative Pd→B interaction in a series of R DPB R' Pd 0 and Pd II complexes ( R DPB R' =( o ‐PR2 C6 H4 )2 BR', diphosphinoborane) was analyzed using XRD, 11 B NMR spectroscopy and NBO/NLMO calculations. The borane acceptor discriminates between the oxidation state Pd II and Pd 0, stabilizing the latter. Reaction of lithium amides with [( R DPB R' )Pd II (4‐NO2 C6 H4 )I] chemoselectively yields the C−N coupling product. DFT modelling indicates no significant impact of Pd II →B coordination on the inner‐sphere reductive elimination rate. Abstract : Ligand effects : The borane acceptor in diphosphinoborane ligands discriminates between the oxidation state Pd II and Pd 0, stabilizing the latter. The impact of the Pd→B interaction on inner‐sphere C−N bond reductive elimination of N, N ‐dimethyl‐4‐nitroaniline was investigated (see scheme).