10534-89-1Relevant articles and documents
Cationic cobaltammines as anion receptors: Synthesis and characterization of [Co(NH3)6](4-np)3.4H2O, [Co(NH3)6](2,4-dnp)3 and [Co(NH 3)6](2,4,6-tnp)3
Sharma, Raj Pal,Bala, Ritu,Sharma, Rajni,Venugopalan, Paloth
, p. 170 - 177 (2005)
In an effort to utilize [Co(NH3)6]3+ cation as a new host for mono-, di- and tri-substituted nitrophenolate anions, yellow solids of composition [Co(NH3)6](4-np) 3.4H2O, [Co(NH3)6](2,4-dnp) 3, and [Co(NH3)6](2,4,6-tnp)3 were obtained in high yields by reacting sodium salts of 4-np, 2,4-dnp and 2,4,6-tnp (where np=nitrophenolate, dnp=dinitrophenolate and tnp=trinitrophenolate,) with [Co(NH3)6]Cl3 respectively in 3:1 molar ratio in hot aqueous medium. These cobalt(III) complex salts have been characterized by elemental analyses and spectroscopic techniques (UV/Visible, IR and NMR). Single crystal X-ray structure determination of [Co(NH3) 6](4-np)3.4H2O revealed the presence of discrete ions, [Co(NH3)6]3+ and C 6H4NO3- in addition to four lattice water molecules in the solid state. A strong network of hydrogen bond interactions (N-H?O (phenolate), N-H?O (nitro), O-H?O (water) stabilize the crystal lattice. The formation of these salts and measurement of solubility products suggests that [Co(NH3) 6]3+ present in [Co(NH3)6]Cl 3 may be used as anion receptor for the nitrophenolate ions.
Role of second-sphere coordination in anion binding: Synthesis, characterization and X-ray structure of hexaamminecobalt(III) chloride hydrogen phthalate trihydrate and sodium hexaamminecobalt(III) benzoate monohydrate
Sharma, Raj Pal,Bala, Ritu,Sharma, Rajni,Kariuki,Rychlewska, Urszula,Warzajtis, Beata
, p. 143 - 151 (2005)
In an effort to utilize [Co(NH3)6]3+cation as a new host for carboxylate ions, orange coloured crystalline solids of composition [Co(NH3)6]Cl(C8H5O 4)2·3H2O (1) and Na[Co(NH 3)6](C7H5O2) 4·H2O (2) were obtained by reacting hot aqueous solutions of hexaamminecobalt(III) chloride with potassium hydrogen phthalate and sodium benzoate in 1:3 molar ratio, respectively. The title complex salts were characterized by elemental analyses and spectroscopic studies (IR, UV/Visible and NMR). Single crystal X-ray structure determinations revealed the formation of second-sphere coordination complexes based on hydrogen bond interactions. In complex salt 1 only two out of three ionisable chloride ions present in [Co(NH3)6]Cl3 were replaced by two C8H5O4- ions whereas in complex salt 2 all the three ionisable chloride ions present in [Co(NH3)6]Cl3 were replaced and the final product was an adduct with another mole of sodium benzoate in solid state. The crystal lattice is stabilized by electrostatic forces of attraction and predominantly N-H?O interactions.
KINETICS AND PHOTOEFFECTS OF OXIDATION AND REDUCTION OF HEXAAMMINECOBALT COMPLEX IN ALKALINE MEDIA.
Ogura,Fukushima
, p. 93 - 97 (1981)
Cyclic voltammograms of hexaamminecobalt complex have been measured in high pH solutions. The spectroscopic result suggested that hydroxoamminecobalt complex adsorbed on the electrode surface during cathodic polarization, and this species grew to form cobalt hydroxide after a long time of electrolysis. Based on these results, the reaction mechanism is discussed. The effect of light on the electrode process has been studied by irradiating with ultraviolet light of the 254 nm mercury resonance line. It is indicated that the hydroxoammine complex is decomposed to cobalt hydroxide and free ligand under light.
Influence of the metal centers on the pKa of the pyrrole hydrogen of imidazole complexes of (NH3)5M3+, M(III) = Co(III), Rh(III), Ir(III), Ru(III)
Fazlul Hoq,Shepherd, Rex E.
, p. 1851 - 1858 (2008/10/08)
The pKa's at 298 K, μ = 0.10 (NaCl), and the temperature dependence (273-343 K) for the deprotonation of the pyrrole NH of several imidazoles coordinated to (NH3)5M3+ moieties (M = CoIII, RhIII, IrIII, RuIII) are reported. A greater importance of dn configuration over ion size is found. Data summarized for various systems are as follows (ligand, M (pK298, ΔHa° in kcal/mol, ΔSa° in eu)): imidazole = imH, CoIII (9.99, 14.0 ± 0.5, 1.3 ± 1.6), RhIII (9.97, 13.6 ± 0.3, 0.1 ± 1.3), IrIII (10.05, 13.4 ± 0.3, 1.2 ± 1.0), RuIII (8.9, 10.0 ± 0.8, 3.7 ± 1.2); 2-methylimidazole = 2-MeimH, CoIII (10.67, 17.8 ± 0.7, 11.2 ± 2.4); 2,4(5)-dimethylimidazole = 2,5-Me2imH, CoIII (11.04, 13.4 ± 0.5, 5.3 ± 1.6), RuIII (10.20, 13.2 ± 0.6, -2.1 ± 1.6). 1H NMR spectra of low-spin d6 complexes of imidazoles and ring-methylated imidazoles are discussed for CoIII, RhIII, IrIII, and RuIII. C-2 and remote ring, C-5, substituents are shifted downfield relative to the free imidazole ligand in the order H+ > CoIII > RhIII > IrIII. The C-4 position is influenced competitively by σ-withdrawal ring substituents and TIP effects for CoIII. Assignments of the remote isomer for (NH3)5M(2,5-Me2imH)3+ (M = CoIII, RuIII) are made from the 1H NMR spectra of the CoIII and RuII complexes. The RuIII complexes of 2,5-Me2imH and the imidazolate form (2,5-Me2im-) both exhibit LMCT spectra. The imidazolato form has three bands at 655, 377, and 272 nm, proposed for II1 → IId, II2 → IId, and n → IId transitions, where II1, II2, and n are the highest HOMO's of the imidazolato ring.