Synthesis and structure of aminocarboxylato(1,4-diaminobutane)dinitrocobalt(III) complexes. Crystal and molecular structure of the δ-(—)589- CIS(NO2)trans(NH2)-(R-alaninato)(1,4-diaminobutane)dinitrocobalt(III) diastereomer.

Nitrosation with Sodium Hexanitrocobaltate(III)

“…14 We were aware of numerous examples where SHNC was employed for the synthesis of various Co(III) complexes by the displacement of the nitro groups by amine ligands using ammonia, 15 monodentate, bidentate, or multidentate amines, 16 amino acids, 17 or the mixture of an amine and an amino acid. 18 The nitrosation of the amine function of those substrates with SHNC was not observed. Our preliminary experiments with primary aliphatic amines (isopropylamine, n-butylamine, tert- 1, encouraged us to extend our work to aromatic amines.…”

“…We were aware of numerous examples where SHNC was employed for the synthesis of various Co(III) complexes by the displacement of the nitro groups by amine ligands using ammonia, monodentate, bidentate, or multidentate amines, amino acids, or the mixture of an amine and an amino acid …”

“…On the other hand, a displacement of NO 2 - ligands with primary aliphatic amines in SHNC seems to give Co 3+ complexes; nitrite ions, which are liberated, do not act as nitrosating entities. SHNC is a reported starting material for the preparation of stable Co 3+ complexes with aliphatic amines possessing primary and/or secondary amino groups. 16c,, This also explains our inability to use SHNC for the nitrosation of diaryl or dialkyl amines. Namely, diphenylamine did not react with SHNC, but diisobutylamine, dicyclohexylamine and piperidine were found to form the corresponding Co 3+ complexes, from which the amines were recovered as described above for primary amines.…”