Selective complexation of α-amino acids and simple peptides via their carboxylate groups

The complexation of anions of selected α-amino acids (alanine, valine, proline, tyrosine) and small peptides (L-alanyl-L-alanine, L-alanyl-L-alanyl-L-alanine, and L-alanyl-L-alanyl-L-alanyl-L-alanine) by the dinuclear nickel(II) complex [LNi2(μ-Cl)]+ (1), where (L)2− represents a 24-membered binucleating hexamine-dithiophenolato ligand, has been investigated. The following complexes were prepared, isolated as perchlorate or tetraphenylborate salts, and characterized by UV/Vis, IR, and CD spectroscopy: [LNi2(μ-L-alaninato)]+ (2), [LNi2(μ-L-valinato)]+ (3), [LNi2(μ-L-prolinato)]+ (4), [LNi2(μ-L-tyrosinato)]+ (5a), [LNi2(μ-D-tyrosinato)]+ (5b), [LNi2(μ-L,D-tyrosinato)]+ (5c), [LNi2(μ-L-alanyl-L-alaninato)]+ (6), [LNi2(μ-(L-alanyl)2-L-alaninato)]+ (7), [LNi2(μ-(L-alanyl)3-L-alaninato)]+ (8). Compounds 4, 5a and 6 were additionally identified by X-ray crystallography. In contrast to unsupported amino carboxylate complexes which typically contain five membered NO chelate rings, the [LNi2]2+ fragment selectively binds the α-amino acids and peptides via μ1,3-bridging carboxylato groups. Coordination of the carboxylato coligands in this way confers dissymmetry on the complexes. The CD spectra of the syn,syn-bridged structures are significantly different from those of the NO chelates, and can distinguish between the two coordination modes. The encapsulation of the peptides increases their solubility in the solvent system MeOH–MeCN by up to two orders of magnitude. This is discussed in terms of the absence of intermolecular hydrogen bonding interactions as indicated in the X-ray structure of 6.