Using J_PP to Identify Ni Bidentate Phosphine Complexes In Situ

Identifying intermediates of Ni-containing reactions can be challenging due to the high reactivity of Ni complexes and their sensitivity toward air and moisture. Many Ni bidentate phosphine complexes are diamagnetic and can be analyzed in situ via ³¹P NMR spectroscopy, but the oxidation state of Ni is difficult to determine using ³¹P chemical shift analysis alone. The J-coupling between P atoms, J_PP, has been proposed to correlate with oxidation state, but few investigations have looked at how J_PP is affected by parameters such as length of the linker or identity of the phosphine or other ligands. The present investigation into the J_PP values of Ni bidentate phosphine complexes with two-carbon and three-carbon linkers shows that the J_PP values observed in ³¹P NMR spectra, |J_PP|, are competent indicators of the oxidation state at Ni. For complexes with two-carbon linkers, |J_PP| > 40 Hz is typical of Ni⁰ while |J_PP| < 30 Hz is typical of Ni^II; this trend is reversed for complexes with three-carbon linkers. Additionally, the Lewis acidity of the Ni and Lewis basicity of the phosphine ligand affect J_PP predictably. For example, increased P-to-Ni donation arising from more-donating phosphines or more-withdrawing ligands trans to the P atoms causes a more negative J_PP. These results should enable the oxidation state of Ni and properties of ligands in Ni bidentate phosphine complexes to be determined in situ during reactions containing these species.