Mass-spectroscopy of polynuclear palladium carboxylate complexes as a key to new structures. Synthesis and X-Ray structure of Pd12(μ-CO)8(μ-NO2)8(μ-iPrCO2)8

Palladium NOx-containing polynuclear carboxylate complexes Pd4(μ-CO)2(μ-NO)(μ-iPrCO2)5 and Pd8(μ-CO)4(μ-NO2)4(μ-iPrCO2)8 were studied with MALDI-TOF mass-spectroscopic technique. The results confirm previous suggestion about Pd4 metal chains as building blocks for big palladium carbonyl carboxylate clusters. Also a new Pd3 bent metal chain observed in mass-spectra was demonstrated to serve a building block as well. Using the data the biggest palladium carboxylate cluster Pd12(μ-CO)8(μ-NO2)8(μ-iPrCO2)8 was synthesized and characterized by X-Ray analysis. Thus it was shown that mass-spectroscopic data for palladium carboxylates can be used for prediction of new structures of palladium clusters.

Palladium NOx-containing polynuclear carboxylate complexes Pd4(μ-CO)(μ-NO)(μ-iPrCO2)5 and Pd8(μ-CO)4(μ-NO2)4(μ-iPrCO2)8 were studied with MALDI-TOF mass-spectroscopic technique. A new Pd3 bent metal chain observed in mass-spectra was demonstrated to serve a building block as well. Using the data the biggest palladium carboxylate cluster Pd12(μ-CO)8(μ-NO2)8(μ-iPrCO2)8 was synthesized and characterized by X-Ray analysis.Figure optionsDownload as PowerPoint slideHighlights
► MALDI-TOF MS-study of Pd4(CO)2(NO)(RCO2)5 and Pd8(CO)4(NO2)4(RCO2)8 clusters was carried out.
► New high-stable fragment of palladium carboxylate clusters – bent Pd3-chain – was observed.
► New approach to synthesis of high-nuclear palladium carboxylate cluster was proposed and tested.
► The biggest palladium carboxylate cluster Pd12(CO)8(NO2)8(RCO2)8 was characterized by X-Ray diffraction analysis.