X-ray and optical studies of one-dimensional bis(dimethylglyoximato)Pd(II), Pd(dmg)₂at high pressures

DFT Investigation of the Molecular Properties of the Dimethylglyoximato Complexes [M(Hdmg)2] (M = Ni, Pd, Pt)

“…Thus, all three complexes form extensive stacks with relatively short M ... M distances of 3.24 (Ni) [4,10,11,14,19,24], 3.25 (Pd) [13,19], or 3.26 Å (Pt) [10,12,13,20], respectively in their solid structures with neighbouring molecules being rotated by almost 90° to allow room for the CH3 groups (collected structural data in Table S1, Supplementary Materials). Pressure experiments have shown that the M ... M interactions account also for the compressibility of these structures and the pressure-dependent changes of colour and electronic properties [3,4,8,12,[26][27][28][29][30][31]. These virtually insoluble metal ... metal stacked solids are the basis for applications of the three compounds [M(Hdmg)2] (M = Pt, Pd, Ni) for the extraction or removal of these elements [32][33][34][35], as components of solid catalysts [36][37][38][39][40], as solid but easily evaporable precursors [37][38][39][40][41][42][43][44][45][46]…”

“…We compared our calculated results with available experimental data and results from similar DFT studies with different functionals and basis sets and thus also provide an overview of the present state of knowledge. Pressure experiments have shown that the M ... M interactions account also for the compressibility of these structures and the pressure-dependent changes of colour and electronic properties [3,4,8,12,[26][27][28][29][30][31]. These virtually insoluble metal ... metal stacked solids are the basis for applications of the three compounds [M(Hdmg) 2 ] (M = Pt, Pd, Ni) for the extraction or removal of these elements [32][33][34][35], as components of solid catalysts [36][37][38][39][40], as solid but easily evaporable precursors [37][38][39][40][41][42][43][44][45][46][47], and in optical devices (e.g., pressure calibrants/indicators) [3,4,12,[26][27][28][29][30][31][48][49][50][51].…”