Template synthesis of N2S and N3S chelates via alkylation of bis(2-aminoethanethiolato)Ni: sulfur- and nitrogen-centered alkylations

Alkylation of bis(2-aminoethanethiolato)nickel(II) (1) occurs strictly at sulfur upon addition of 2-bromoethylamine and iodoacetamide to yield (2-[(2-aminoethyl)thio]ethaneamine)nickel(II)bromide, [(DAES)2Ni]Br2 (2), and (2-[(2-amino-2-oxoethyl)thio]acetamide)nickel(II)iodide, [(AOTA)2Ni]I2 (4), respectively. Reaction with chloroacetamide yields the sulfur- and nitrogen-alkylated product (2-[(2-aminoethyl)thio]acetamide)nickel(II)chloride, (AETA)NiCl2 (3a) with dissociation of the second aminoethanethiolato ligand. A pathway is proposed consistent with the leaving group dependence.