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Evaluation of Pd?B Interactions in Diphosphinoborane Complexes and Impact on Inner-Sphere Reductive Elimination.

ABSTRACT: The dative Pd?B interaction in a series of R DPBR' Pd0 and PdII complexes (R DPBR' =(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 PdII and Pd0 , stabilizing the latter. Reaction of lithium amides with [(R DPBR' )PdII (4-NO2 C6 H4 )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.

SUBMITTER: Ritter F 

PROVIDER: S-EPMC7692930 | biostudies-literature | 2020 Oct

REPOSITORIES: biostudies-literature

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

Ritter Florian F   John Lukas L   Schindler Tobias T   Schroers Julian P JP   Teeuwen Simon S   Tauchert Michael E ME  

Chemistry (Weinheim an der Bergstrasse, Germany) 20200918 59

The dative Pd→B interaction in a series of <sup>R</sup> DPB<sup>R'</sup> Pd<sup>0</sup> and Pd<sup>II</sup> complexes (<sup>R</sup> DPB<sup>R'</sup> =(o-PR<sub>2</sub> C<sub>6</sub> H<sub>4</sub> )<sub>2</sub> BR', diphosphinoborane) was analyzed using XRD, <sup>11</sup> B NMR spectroscopy and NBO/NLMO calculations. The borane acceptor discriminates between the oxidation state Pd<sup>II</sup> and Pd<sup>0</sup> , stabilizing the latter. Reaction of lithium amides with [(<sup>R</sup> DPB<sup>R'</  ...[more]

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