Addition of two equivalents of dimesityl phosphine (PHMes2) to anhydrous NiX2 (X = I, Br, Cl) yielded [Ni(PHMes2)2X2] (X = I (1), Br (2), Cl (3)). Recrystallized samples were analyzed by X-ray crystallography and showed that 1-3 crystallized as the trans isomer in the solid state. This isomer is also present in solution for 1 and 2 based on observation and simulation of the second order AA’XX’ coupling in 31P and 1H NMR spectra. Similar NMR experiments were performed on 3, however the results were less clear. Variable Temperature 31P{1H} NMR ranging from -40°C to 60°C was performed on 3. Two signals were observed at lower temperatures, along with PHMes2. We are currently working on identifying whether this is indicative of paramagnetism, dynamic ligand exchange, and/or fast isomerization on the NMR time scale.

Synthesis of monometallic nickel (II) halide complexes with secondary phosphines as building blocks for hydrogenase mimics

253rd National Meeting (2017)

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