Palladium(IV) in an Oxoanionic Environment: The XeF₂ Assisted Synthesis of [Pd(S₂O₇)₃]²⁻

Abstract

For the first time tetravalent palladium is detected, coordinated exclusively by simple oxoanions. Stabilization was achieved by formation of the [Pd(S2 O7 )3 ](2-) complex in which three chelating disulfate groups surround the metal atom. The salt K2 [Pd(S2 O7 )3 ] could only be obtained if the reaction of K2 [PdCl6 ] and neat SO3 was performed in the presence of XeF2 .

From S–O–S to B–O–S to B–O–B Bridges: Ba[B(S2O7)2]2 as a Model System for the Structural Diversity in Borosulfate Chemistry

“…The bands at 785, 760, 723, and 710 cm –1 can be assigned to stretching vibrations ν­(S–O b ) and thus prove the presence of S–O–S bridges. This is well in accordance with previous calculations on the disulfates K 2 [Pd­(S 2 O 7 ) 3 ] and A 2 [ M (S 2 O 7 ) 3 ] ( A = NH 4 , Ag; M = Si, Ge, Sn) . The region below 650 cm –1 is dominated by bending vibrations δ­(O–B–O) and δ­(O–S–O).…”

Sr[B2(SO4)3(S2O7)]: A Borosulfate with an Unprecedented Chain Structure Comprising Disulfate Groups

“…The presence of the S–O–S bridges could be confirmed by the bands at 781, 752, and 701 cm –1 , which are assigned to stretching vibrations ν­(S–O b ) involving the bridging oxygen atom of the disulfate group. This is also in good agreement with previous calculations on disulfates. , Below 650 cm –1 , predominately bending vibrations of δ­(O–B–O) and δ­(O–S–O) occur.…”

Crystal Structures of the High‐Pressure Palladium Dichalcogenides Pd0.94(1)S2 and Pd0.88(1)Se2 Comprising Exceptional PdIV Oxidation States

“…The rutile‐type PdO 2 for example prepared at high oxygen pressures was recently described as unstable at ambient conditions . Typically, only strong oxidation agents like fluorine (PdF 4 and [PdF 6 ] – salts), other halogens in terms of palladates A 2 [Pd X 6 ] ( A = NH 4 + , K, Rb, Cs; X = Cl, Br, I) or pure SO 3 in presence of XeF 2 (K 2 [Pd(S 2 O 7 ) 3 ]) can oxidize Pd to its fourfold oxidation state. All the more astonishing is that Pd 4+ oxidation states can be generated by sulfur or selenium, if pressure is applied.…”

“…[31] Interestingly, the interhalogen bonding gets lost during this pressure-induced redox reaction accompanied by a structural change from tetragonal to a cubic arrangement, whereas the chalcogen dumbbells in HP-Pd 1-x Q 2 (Q = S, Se) are not significantly affected in their bond length by the structural change and the partial palladium oxidation. For a comprehensive literature review concerning Pd 4+ in an oxoanionic environment, the reader is referred to a recent published work by Bruns et al [32]…”