[Pd₈(CH₃COO)₈(NO)₈]: solution from X-ray powder diffraction data

Abstract

The water-insoluble title compound, octakis(mu-acetato-kappa2O:O)octakis(mu-nitroso-kappa2N:O)octapalladium(II), [Pd8(CH3COO)8(NO)8], was precipitated as a yellow powder from a solution of palladium nitrate in nitric acid by adding acetic acid. Ab initio crystal structure determination was carried out using X-ray powder diffraction techniques. Patterson and Fourier syntheses were used for atom locations, and the Rietveld technique was used for the final structure refinement. The crystal structure is of a molecular type. The skeleton of the [Pd8(CH3COO)8(NO)8] molecule is constructed as a tetragonal prism with Pd atoms at the vertices. The eight NO- groups are in bridging positions along the horizontal edges of the prism. The N and O atoms of each nitroso group coordinate two different Pd atoms. The vertical edges present PdPd contacts with a short distance of 2.865 (1) A. These Pd atoms are bridged by a pair of acetate groups in a cis orientation with respect to each other. The complex has crystallographically imposed 4/m symmetry; all C atoms of the acetate groups are on mirror planes. The unique Pd atom lies in a general position and has square-planar coordination, consisting of three O and one N atom.

Secondary building units, nets and bonding in the chemistry of metal–organic frameworks

“…62). 157 In each square, the Pd atoms are bridged by NO ligands. The two squares are bridged by eight carboxylates, two per Pd corner.…”

Microwave-Assisted Solvent Extraction of Inert Platinum Group Metals from HNO3(aq) to Betainium-Based Thermomorphic Ionic Liquid

“…In a similar manner, [Pd 2 (bet) 4 ] 4+ could be formed instead of the mononuclear [Pd­(bet) 2 ] 2+ simply predictable from the estimated slope in Figure b. Although these matters currently discussed are just hypotheses to explain the slope analyses resulted from Figure b, the syn–syn bridging coordination mode of carboxylates is quite usually observed in polynuclear complexes of various transition metal ions including PGMs. − To clarify this point, an EXAFS study should be one of our next tasks, because this method will provide helpful information to judge whether or not an M···M interaction arising from the polynucleation is present in the extractable species of PGMs.…”

Porous Organic Polymers Containing Active Metal Centers for Suzuki–Miyaura Heterocoupling Reactions

“…The WAXS patterns of Pd-supported catalysts, depicted in Figure , showed very weak reflections around 12 and 33°, which could come from Pd­(OAc) 2 . Comparing the amorphous halos of Pd@SP-POPs with those corresponding to the precursor porous polymers, significant changes in the patterns were observed, especially in Pd@SP-POP1 and Pd@SP-POP2.…”