Structural variation in cerium aryloxide complexes templated by hemilabile K⁺–amine interactions

Abstract

bdmmp = (bis(dimethylamino)methyl-4-phenolate)) are presented. The complexes were obtained through metathesis and protonolysis reactions from K[Ce(OTf)(bdmmp) 3 ] or K[Ce(OtBu)(bdmmp) 3 ]respectively. X-ray diffraction studies provide insight into the effect of the steric profile of the aryloxide ligand on perturbing the templating effect of the K + ion with the pendent tertiary amine groups of the bdmmp À ligands. Characterization of the various aryloxide derivatives through cyclic voltammetry and variable temperature 1 H NMR studies demonstrate the impact of the substituents on the solution dynamics and redox properties. Additionally, an unusual example of a terminal cerium(III) hydroxide complex was isolated and characterized in solid state and in solution using the bdmmp framework.

1,2-Addition or Enolization? Variable Reactivity of a Cerium Acetylide Complex toward Carbonyl Compounds

“…The corresponding Ce(1)–O(4) bond length (2.268(3) Å) was notably shortened compared to Ce(1)–O bdmmp bond distances (2.3485(13)–2.3690(13) Å) and is consistent with those reported for the Ce III alkoxide bond distances (Table ). ,, The short C(41)–C(42) distance (1.184(10) Å) is consistent with the triple bond being retained at the former phenylacetylene fragment.…”

“… 12,14,20. The short C(41)−C(42) distance (1.184(10) Å) is consistent with the triple bond being retained at the former phenylacetylene fragment.…”

“…Recently, we employed a flexible polydentate ligand framework, 2,6-bis(dimethylamino)-4-methylphenolate (bdmmp − ), 11 for investigation of the impact of the substituents on the solution dynamics and redox properties in a series of cerium-bdmmp aryloxides. 12 We also use the bdmmp framework in the stabilization, isolation, and structural characterization of the first thermally stable terminal trivalent cerium acetylide, Na[Ce(CCPh)(bdmmp) 3 ] (1, Scheme 1). 13 It was shown that the reaction of complex 1 with acetophenone (pK a DMSO = 24.7) resulted in the formation of a propargylic alkoxide coordinated to the cerium(III) cation, Na[Ce(OC(Me)(Ph)CCPh)(bdmmp) 3 ] (2).…”

“…The scarcity of structural information about organocerium compounds featuring Ce–C σ-bonds precludes a comprehensive understanding of their reactivity, selectivity, and functional group tolerance. Recently, we employed a flexible polydentate ligand framework, 2,6-bis­(dimethylamino)-4-methylphenolate (bdmmp – ), for investigation of the impact of the substituents on the solution dynamics and redox properties in a series of cerium-bdmmp aryloxides . We also use the bdmmp framework in the stabilization, isolation, and structural characterization of the first thermally stable terminal trivalent cerium acetylide, Na­[Ce­(CCPh)­(bdmmp) 3 ] ( 1 , Scheme ).…”

Electrochemical Performance of Transition Metal‐Coordinated Polypyrrole: A Mini Review

“…[25,26] Similarly, PPymodified titanium foam electrode also could exhibit high capacitance of 855 F g À1 at 1.0 A g À1 and keep capacitance retention ratio of 81.1 % after 1000 cycles in 0.5 M K 2 SO 4 electrolyte. [27] In addition, the electrochemical performance of metallic-coordinated PPy supercapacitor is superior to the [a] Y. Xie School of Chemistry and Chemical Engineering Southeast University Nanjing 211189, China E-mail: ybxie@seu.edu.cn previously reported PPy composites, such as 56 Wh kg À1 for polypyrrole/activated carbon supercapacitors, [28] 29 Wh kg À1 for polypyrrole nanotube supercapacitor, [29] and 11 Wh kg À1 for polypyrrole/graphene oxide/ZnO supercapacitor. [30] Table 1 lists the electrochemical stability of the referred polypyrrole electrode materials and the metallic-coordinated polypyrrole.…”