Pd4+ in oxoanionischer Umgebung: Die XeF2‐unterstützte Synthese von [Pd(S2O7)3]2−

Bruns, Jörn; Gerven, David van; Klüner, Thorsten; Wickleder, Ma­thias S.

doi:10.1002/ange.201601767

Cited by 4 publications

(2 citation statements)

References 61 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In course of our investigations of the H 2 SO 4 /SO 3 system we reported several important findings. Firstly, the extraordinary oxidation power could be shown by the oxidation of platinum metals leading to several unique compounds [20–30] . Secondly, we could demonstrate that the assumed infinite chain growth of polysulfuric acids H 2 S n O 3 n +1 , that is with increasing SO 3 content, is doubtful [31,32] .…”

Section: Introductionmentioning

confidence: 88%

“…Firstly, the extraordinary oxidation power could be shown by the oxidation of platinum metals leading to several unique compounds. [20][21][22][23][24][25][26][27][28][29][30] Secondly, we could demonstrate that the assumed infinite chain growth of polysulfuric acids H 2 S n O 3n + 1 , that is with increasing SO 3 content, is doubtful. [31,32] Nevertheless, the assumption that the Brønsted acidity of H 2 SO 4 /SO 3 mixtures increases with increasing SO 3 content seems reasonable.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Stabilizing the Homopolycation (I₄)²⁺ with a Hexasulfate in (I₄)[S₆O₁₉] and a Borosulfate in (I₄)[B(S₂O₇)₂]₂

et al. 2022

Self Cite

View full text Add to dashboard Cite

The reaction of elemental iodine and SO 3 in a sealed glass ampoule yielded a turquoise‐colored solution. At temperatures below 7 °C, deep red crystals of (I 4 )[S 6 O 19 ] grow. With the addition of B 2 O 3 and pyridine‐SO 3 complex red crystals of (I 4 )[B(S 2 O 7 ) 2 ] 2 can be obtained after heating the mixture to 120 °C. The combination of an (I 4 ) 2+ cation with oxoanions has previously not been observed. Both anions have a significant but different influence on the structural properties of the (I 4 ) 2+ cation.

show abstract

Section: Introductionmentioning

confidence: 88%

Section: Introductionmentioning

confidence: 99%

Stabilizing the Homopolycation (I₄)²⁺ with a Hexasulfate in (I₄)[S₆O₁₉] and a Borosulfate in (I₄)[B(S₂O₇)₂]₂

et al. 2022

Self Cite

View full text Add to dashboard Cite

show abstract

Synthesis, Structure, and Reductive Elimination of Cationic Monoarylpalladium(IV) Complexes Supported by a Tripodal Oxygen Ligand

Au-yeung

Sung

et al. 2017

Eur J Inorg Chem

View full text Add to dashboard Cite

Cationic monoaryl-Pd IV complexes supported by the Kläui tripodal ligand [Co(η 5 -C 5 H 5 ){P(O)(OEt) 2 } 3 ] -(L OEt -) were synthesized, and their reductive elimination was studied. Treatment of trans-[Pd(PPh 3 ) 2 (Ar)(I)] and [{Pd(η 2 -ppytBu)Cl} 2 ] [ppyt-BuH = 2-(4-tert-butylphenyl)pyridine] with [AgL OEt ] afforded [Pd(Ar)(PPh 3 )(η 2 -L OEt )] [Ar = Ph (1), p-tolyl (2)] and [Pd(η 2 -ppytBu)(η 2 -L OEt )] (3), respectively. 2928 (L OEt )](PF 6 ) (6), respectively. Complexes 4 and 5 underwent C(sp 2 )-Cl elimination at 40°C in acetonitrile to give a Pd II -L OEt species and the corresponding chloroarene. On the other hand, the C(sp 2 )-Cl elimination of 6 occurred at room temperature and afforded a Pd II species, presumably [Pd(ClppytBuH)-(L OEt )](PF 6 ), which further reacted with PhICl 2 to yield [Pd-(η 2 -ClppytBu)Cl(L OEt )](PF 6 ) (7) [ClppytBuH = 2-(4-tert-butyl-2chlorophenyl)pyridine]. The structures of complexes 1, 4, 6, and 7 were established by X-ray crystallography.Despite the wealth of organometallic chemistry of Pd 0 and Pd II , [5] the coligand effect on the reactivity of Pd IV complexes has not been well explored. Chelating coligands can increase the electron density of the Pd center, and thus facilitate Pd II / Pd IV oxidation and enhance the chemo-and regioselectivity of Pd-mediated C-H transformations. Of special interest are facially coordinating tridentate ligands, which have proven to be excellent spectator ligands for Pd IV . [2] Although Pd-based catalysts in oxygen-rich ligand environments [e.g., palladium(II) acetate and oxide] are well known, [1,6] not many well-defined organo-Pd IV complexes with O-donor ligands have been synthesized; [7] reported Pd IV complexes are mostly supported by N-and C-donor ligands. [2,8] We are particularly interested in Kläui's tripodal ligand [CoCp{P(O)(OEt) 2 } 3 ] -(Cp = η 5 -C 5 H 5 ; denoted L OEt hereafter; Scheme 2), which is capable of stabilizing metal ions in high oxidation states. [9] The synthesis of stable high-valent transition metal (e.g., Ru VI ), [9b,10a-10d] and lanthanide (Ce IV ) [10e] complexes of L OEt suggests that the {PdL OEt } fragment can serve as a good platform for the study of Pd IV organometallic chemistry. Previously, Kläui and co-workers synthesized Pd II complexes with bidentate L OR -(R = Me, Et) ligands, for example, [(η 2 -L OMe )Pd(allyl)] and [(η 2 -L OMe )Pd(PPh 3 )Cl]. [11] Nevertheless, the oxidative addition of these Pd II -L OMe complexes has not been reported. The trialkyl-Pd IV complexes [(L OMe )Pd(Me) 2 R] were obtained by oxidative addition of [Pd(bpy)Me 2 ] (bpy = 2,2′-bipyridine) with RI in the presence of [NaL Ome ]/[AgL Ome ]; [12] however, like other trialkyl-Pd IV complexes, [(L OMe )Pd(Me) 2 R] do not undergo reductive elimination. To enhance the reactivity of the Pd IV center, we sought to synthesize monoaryl-Pd IV -L OEt halide complexes. Herein, we describe the synthesis of cationic Pd IV -L OEt aryl com-Eur.

show abstract

Crystal Structures of the High‐Pressure Palladium Dichalcogenides Pd_0.94(1)S₂ and Pd_0.88(1)Se₂ Comprising Exceptional Pd^IV Oxidation States

Selb

Götsch

Janka

et al. 2017

Zeitschrift anorg allge chemie

View full text Add to dashboard Cite

Abstract. Metastable palladium deficient high-pressure phases with the compositions Pd 1-x S 2 and Pd 1-x Se 2 could be obtained via highpressure/high-temperature syntheses at 7.5 GPa (Pd 0.88(1) Se 2 ) and 11.5 GPa (Pd 0.94(1) S 2 ) at 1523 K. Compared to the normal-pressure modifications they showed a significant decrease in the c-lattice parameters of Δc/c = 4.4 % (Pd 0.94(1) S 2 ) and Δc/c = 10.8 % (Pd 0.88(1) Se 2 ) accompanied by under-occupied palladium sites. Singlecrystal analyses indicated the space group Pbca with lattice parameters

show abstract

Pd⁴⁺ in oxoanionischer Umgebung: Die XeF₂‐unterstützte Synthese von [Pd(S₂O₇)₃]²⁻

Cited by 4 publications

References 61 publications

Stabilizing the Homopolycation (I₄)²⁺ with a Hexasulfate in (I₄)[S₆O₁₉] and a Borosulfate in (I₄)[B(S₂O₇)₂]₂

Stabilizing the Homopolycation (I₄)²⁺ with a Hexasulfate in (I₄)[S₆O₁₉] and a Borosulfate in (I₄)[B(S₂O₇)₂]₂

Synthesis, Structure, and Reductive Elimination of Cationic Monoarylpalladium(IV) Complexes Supported by a Tripodal Oxygen Ligand

Crystal Structures of the High‐Pressure Palladium Dichalcogenides Pd_0.94(1)S₂ and Pd_0.88(1)Se₂ Comprising Exceptional Pd^IV Oxidation States

Contact Info

Product

Resources

About

Pd4+ in oxoanionischer Umgebung: Die XeF2‐unterstützte Synthese von [Pd(S2O7)3]2−

Cited by 4 publications

References 61 publications

Stabilizing the Homopolycation (I4)2+ with a Hexasulfate in (I4)[S6O19] and a Borosulfate in (I4)[B(S2O7)2]2

Stabilizing the Homopolycation (I4)2+ with a Hexasulfate in (I4)[S6O19] and a Borosulfate in (I4)[B(S2O7)2]2

Synthesis, Structure, and Reductive Elimination of Cationic Monoarylpalladium(IV) Complexes Supported by a Tripodal Oxygen Ligand

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

Contact Info

Product

Resources

About

Pd⁴⁺ in oxoanionischer Umgebung: Die XeF₂‐unterstützte Synthese von [Pd(S₂O₇)₃]²⁻

Stabilizing the Homopolycation (I₄)²⁺ with a Hexasulfate in (I₄)[S₆O₁₉] and a Borosulfate in (I₄)[B(S₂O₇)₂]₂

Stabilizing the Homopolycation (I₄)²⁺ with a Hexasulfate in (I₄)[S₆O₁₉] and a Borosulfate in (I₄)[B(S₂O₇)₂]₂

Crystal Structures of the High‐Pressure Palladium Dichalcogenides Pd_0.94(1)S₂ and Pd_0.88(1)Se₂ Comprising Exceptional Pd^IV Oxidation States