Experimental and computational exploration of the dynamic behavior of (PNP)BF2, a boron compound supported by an amido/bis(phosphine) pincer ligand

The diarylamido/bis(phosphine) PNP pincer ligand (2-(i)Pr(2)P-4-MeC(6)H(3))(2)N has been evaluated as a scaffold for supporting a BF(2) fragment. Compound (PNP)BF(2) (6) was prepared by simple metathesis of (PNP)Li (5) with Me(2)SBF(3). NMR spectra of 6 in solution are of apparent C(2) symmetry, suggestive of a symmetric environment about boron. However, a combination of X-ray structural studies, low-temperature NMR investigations, and DFT calculations consistently establish that the ground state of this molecule contains a classical four-coordinate boron with a PNBF(2) coordination environment, with one phosphine donor in PNP remaining "free". Fortuitous formation of a single crystal of (PNP)BF(2)·HBF(4) (7), in which the "free" phosphine is protonated, furnished another structure containing the same PNBF(2) environment about boron for comparison and the two PNBF(2) environments in 6 and 7 are virtually identical. DFT studies on several other diarylamido/bis(phosphine) pincer (PNP)BF(2) systems were carried out and all displayed a similar four coordinate PNBF(2) environment in the ground state structures. The symmetric appearance of the room-temperature NMR spectra is explained by the rapid interconversion between two degenerate four-coordinate, C(1)-symmetric ground-state forms. Lineshape analysis of the (1)H and (19)F NMR spectra over a temperature range of 180-243 K yielded the activation parameters ΔH(‡) = 8.1(3) kcal mol(-1) and ΔS(‡) = -6.0(15) eu, which are broadly consistent with the calculated values. Calculations indicate that the exchange of phosphine donors at the boron center proceeds by an intrinsically dissociative mechanism.