Base Hydrolysis of Pentaaminecobalt(III) Complexes: The [CoX(dien) (dapo)]n+ system. Part 1. Syntheses, structures, configuration, and spectroscopy

Oxygentation of aqueous solutions of Co III in presence of stoichiometric amounts of N ‐(2‐aminoethyl)ethane‐1,2‐diamine (dien) and 1,3‐diaminopropan‐2‐ol (dapo) produces μ‐peroxocobalt(III) dimers. Acid cleavage (HCI) yields mer ‐ exo (H)‐, mer ‐ endo (H)‐, unsym ‐ fac ‐ exo (OH)‐, and unsym ‐ fac ‐ endo (OH)‐[CoCl(dien)(dapo)] 2+ ( A–D )(X = Cl), resp. and unsym ‐ fac ‐[Co‐(dien)(dapo‐ N , N ′, O )] 3+ ( G ). Isomer seperation was achieved by fractional crystallization as ZnCl and ClO salts and by ion‐exchange chromatography. The corresponding bromo, azido, nitrito‐ O , nitro‐ N , thiocyanato, hydroxo, and aqua complexes were also synthesized. Optically resolved samples were prepared for chiral compounds, and the complexes were structurally characterized by X‐ray analyses ( {article}{empty}{document}Λ ^ →{document} (−) 436(CD) ‐A (X = N 3 )), ( {article}{empty}{document}Δ ^ →{document} (−) 436 (CD) ‐B ). (X = N 3 ), {article}{empty}{document}Δ ^ →{document} (+) 436 (CD) ‐B by their chiroptical properties, and by 13 C‐NMR spectroscopy supported by 1 H‐NMR, IR, CD, and UV/VIS spectroscopy. {article}{empty}{document}Λ ^ →{document} (−) 436(CD) ‐mer‐exo(H)‐[Co(N 3 )(dien)(dapo)](hydrogen di‐ O ‐benzoyl‐L‐tartrate) 2 .4 H 2 O crystallizes in the orthorhombic space group P2 1 2 1 2 1 , a = 7.676(1) Å, b = 19.457(1) Å, c = 34.702(2) Å. {article}{empty}{document}Λ ^ →{document} (−) 436(CD) ‐mer‐endo(H)‐[Co(N 3 )(dien)(dapo)] (hydrogen di‐ O ‐benzoyl‐L‐tartrate) 2 .2.75 H 2 O crystallizes in the triclinic space group P 1, a = 8.062(3) Å b = 10.296(1) Å, c = 15.056(2) Å, alpha = 80.55(1)°, β = 85.18(2)°, γ = 89.10(2)°. {article}{empty}{document}Δ ^ →{document} (+) 436(CD) ‐mer‐endo(H)‐[Co(N 3 )(dien)(dapo)](hydrogen di‐ O ‐benzoyl‐L‐tartrate) 2 . 5.75 H 2 O crystallizes in the triclinic space group P 1, a = 7.742(1) Å, b = 10.014(1) Å, c = 18.045(2) Å, α = 99.57(1)°, β = 92.87(1)°, γ = 102.56(1)°. The absolute configurations of the three cations were determined unambiguously. Interconversions of the various isomers and derivatives and structural, configurational, and spectroscopic aspects are discussed in detail.