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Evaluation of Pd→B Interactions in Diphosphinoborane Complexes and Impact on Inner‐Sphere Reductive Elimination

The dative Pd→B interaction in a series of RDPBR’ Pd0 and PdII complexes (RDPBR’=(o‐PR2C6H4)2BR’, diphosphinoborane) was analyzed using XRD, 11B NMR spectroscopy and NBO/NLMO calculations. The borane acceptor discriminates between the oxidation state PdII and Pd0, stabilizing the latter. Reaction of...

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Published in:Chemistry : a European journal 2020-10, Vol.26 (59), p.13436-13444
Main Authors: Ritter, Florian, John, Lukas, Schindler, Tobias, Schroers, Julian P., Teeuwen, Simon, Tauchert, Michael E.
Format: Article
Language:English
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Summary:The dative Pd→B interaction in a series of RDPBR’ Pd0 and PdII complexes (RDPBR’=(o‐PR2C6H4)2BR’, diphosphinoborane) was analyzed using XRD, 11B NMR spectroscopy and NBO/NLMO calculations. The borane acceptor discriminates between the oxidation state PdII and Pd0, stabilizing the latter. Reaction of lithium amides with [(RDPBR’)PdII(4‐NO2C6H4)I] chemoselectively yields the C−N coupling product. DFT modelling indicates no significant impact of PdII→B coordination on the inner‐sphere reductive elimination rate. Ligand effects: The borane acceptor in diphosphinoborane ligands discriminates between the oxidation state PdII and Pd0, 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).
ISSN:0947-6539
1521-3765
1521-3765
DOI:10.1002/chem.202001189