Evaluation Of Pd -> B Interactions In Diphosphinoborane Complexes And Impact On Inner-Sphere Reductive Elimination

The dative Pd(R)B interaction in a series of(R)DPB(R')Pd(0)and Pd(II)complexes ((R)DPBR'=(o-PR2C6H4)(2)BR', diphosphinoborane) was analyzed using XRD,B-11 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)DPBR')Pd-II(4-NO2C6H4)I] chemoselectively yields the C-N coupling product. DFT modelling indicates no significant impact of Pd-II(R)B coordination on the inner-sphere reductive elimination rate.