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An extensive number of organic sorbents can be used for extraction of precious metals from solutions, among which organosilicon sorbents deserve a particular attention. The sorption activity of organosilicon sorbents is determined by the nature of the functional group and its position in the polymer chain. In this study, the effect of the nature and position of the functional substituent on the sorption activity of polyalkylsilsesquioxanes with respect to Ag (I) and Au (III) ions is analyzed for polymer homologues and polymer analogs with sulfhydril, sulphonic, thioalkylamine, guanidine, biguanidine, malonodiamide and phthalamide groups. It is shown that the sorption activity of the com-pounds under study increases during a transition from polyalkylsilsesquioxanes, containing chemically active groups in the  -position, to their polymer homologues, containing these groups in the  - и  -position. The sorption activity of complexing polymers is determined by the stability of the chelate compounds formed, the number of donor-active atoms in the functional groups and their spatial position facilitating the formation of complexes