We report on the discovery of the first two examples of cationic palladium(II)-oxo clusters (POCs) containing f-metal ions, [Pd II 6 O 12 M 8 {(CH 3 ) 2 AsO 2 } 16 (H 2 O) 8 ] 4 + (M = Ce IV , Th IV ), and their physicochemical characterization in the solid state, in solution and in the gas phase. The molecular structure of the two novel POCs comprises an octahedral {Pd 6 O 12 } 12À core that is capped by eight M IV ions, resulting in a cationic, cubic assembly {Pd 6 O 12 M IV 8 } 20 + , which is coordinated by a total of 16 terminal dimethylarsinate and eight water ligands, resulting in the mixed Pd II -Ce IV /Th IV oxoclusters [Pd II 6 O 12 M 8 {(CH 3 ) 2 AsO 2 } 16 (H 2 O) 8 ] 4 + (M = Ce, Pd 6 Ce 8 ; Th, Pd 6 Th 8). We have also studied the formation of hostguest inclusion complexes of Pd 6 Ce 8 and Pd 6 Th 8 with anionic 4-sulfocalix[n]arenes (n = 4, 6, 8), resulting in the first examples of discrete, enthalpically-driven supramolecular assemblies between large metal-oxo clusters and calixarenebased macrocycles. The POCs were also found to be useful as pre-catalysts for electrocatalytic CO 2 -reduction and HCOOH-oxidation.
We report on the first example of a PdIV-containing polyoxopalladate(II). The discrete mixed-valent polyoxopalladate(IV/II), [PdIVPdII6O6((CH3)2AsO2)6]2-, comprising a central PdIV ion that is surrounded by a six-membered PdII-oxo ring capped by...
We report on the discovery of the first two examples of cationic palladium(II)‐oxo clusters (POCs) containing f‐metal ions, [PdII6O12M8{(CH3)2AsO2}16(H2O)8]4+ (M=CeIV, ThIV), and their physicochemical characterization in the solid state, in solution and in the gas phase. The molecular structure of the two novel POCs comprises an octahedral {Pd6O12}12− core that is capped by eight MIV ions, resulting in a cationic, cubic assembly {Pd6O12MIV8}20+, which is coordinated by a total of 16 terminal dimethylarsinate and eight water ligands, resulting in the mixed PdII‐CeIV/ThIV oxo‐clusters [PdII6O12M8{(CH3)2AsO2}16(H2O)8]4+ (M=Ce, Pd6Ce8; Th, Pd6Th8). We have also studied the formation of host‐guest inclusion complexes of Pd6Ce8 and Pd6Th8 with anionic 4‐sulfocalix[n]arenes (n=4, 6, 8), resulting in the first examples of discrete, enthalpically‐driven supramolecular assemblies between large metal‐oxo clusters and calixarene‐based macrocycles. The POCs were also found to be useful as pre‐catalysts for electrocatalytic CO2‐reduction and HCOOH‐oxidation.
The first discrete mixed platinum(IV)-gold(III) oxoanion [PtIV2AuIII3O6((CH3)2AsO2)6]– (1) was synthesized by reaction of H2Pt(OH)6 with H[AuCl4] in a simple one-pot procedure in aqueous solution at pH 7 and comprises two...
We have discovered the first polythioplatinate(II), [PtII
3S2(SO3)6]10– (1), which was synthesized in aqueous
basic medium
(pH 11) by hydrothermal heating at 150 °C. Polyanion 1 comprises a discrete, triangular assembly of three Pt2+ ions linked by two μ3-sulfido ligands, and their
square-planar coordination geometry is completed by two terminal S-bound
sulfito ligands. Polyanion 1 was isolated as a hydrated
sodium salt, Na10[PtII
3(μ3-S)2(SO3)6]·22H2O (Na-1), which was characterized in the solid
state by single-crystal X-ray diffraction, Fourier-transform infrared
spectroscopy, thermogravimetric analysis, X-ray photoelectron spectra,
and elemental analysis, in solution by 195Pt NMR and atomic
absorption spectroscopy, and in the gas phase by electrospray ionization
mass spectrometry. Density functional theory calculations were performed,
and the 195Pt NMR chemical shifts of 1 were
computed theoretically and shown to match well with the experimental
data. Furthermore, the discrete title polyanion 1 was
immobilized on mesoporous SBA-15 support and used as a precatalyst
for the hydrogenation of o-xylene.
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