SYNTHESIS AND CHARACTERIZATION OF HIGHLY PURE FORM OF SODIUM-SALT OF ANIONIC, THIOMALATOGOLD(I) COMPLEX WITH ANTIARTHRITIC ACTIVITY - ANALOGS OF ANIONIC, THIOMALATOSILVER(I) COMPLEX WITH ANTIMICROBIAL ACTIVITY
K. Nomiya et al., SYNTHESIS AND CHARACTERIZATION OF HIGHLY PURE FORM OF SODIUM-SALT OF ANIONIC, THIOMALATOGOLD(I) COMPLEX WITH ANTIARTHRITIC ACTIVITY - ANALOGS OF ANIONIC, THIOMALATOSILVER(I) COMPLEX WITH ANTIMICROBIAL ACTIVITY, Bulletin of the Chemical Society of Japan, 68(10), 1995, pp. 2875-2883
Sodium salt of anionic Au(I) complex with a trianion of thiomalic acid
tma(3-) (H(3)tma=HOOCCH(SH)CH2COOH), known as an effective antiarthri
tic drug, was prepared in highly pure form by one-step synthesis from
NaAuCl4 and tma(3-) in aqueous solution. The reaction consisted of a r
eduction of Au(III) by tma(3-) and the following complexation of Au(I)
with tma(3-) ligand. The disulfide species of tma(3-) formed by this
reduction was removed by passing through an anion-exchange resin colum
n and the contaminating NaCl by passing through a gel filtration colum
n. The tma-Au(I) complex was also prepared by another reaction based o
n ligand exchange of the intermediate complex AuCl(thiodiglycol) with
tma(3-). It was purified using the anion-exchange resin and gel filtra
tion columns. The target compound, finally isolated in 30% yield in hi
ghly pure form, has been characterized by complete elemental analyses,
TG/DTA, FT-IR, H-1 and C-13 NMR spectroscopies, and molecular weight
was determined in aqueous solution by molmass measurement based on the
cryoscopic method combined with dissociation degree determination bas
ed on the [Naf] measurement in equilibrium state using a Na+-ion selec
tive electrode. This Au(I) complex was an oligomer with a formula of {
Na-2[Au(tma)]. 1.75H(2)O}(n) (n=3-10; MW=1260-4220). This polymerizati
on degree, low in comparison with previously proposed data, was determ
ined in the neutral aqueous solution without any other electrolytes un
der the concentration range C-Na=0.914-182.9 mmol dm(-3). The tma-Au(I
) complex exists in an oligomeric form both in the solid and in aqueou
s solution. The properties of the oligomeric tma-Au(I) complex were co
mpared with those of the previously reported complex and a commerciall
y available sample, and also with those of the recently prepared, olig
omeric tma-Ag(I) complex with antimicrobial activity.