Formed spherical polymeric complexes of metals of the 8th subgroup of the periodic system with ligands of an organosiloxane copolycondensate optionally cross-linked by means of cross-linking agents containing Si, Ti, Zr and/or Al (statistical, block-shaped or mixed). This copolycondensate consists of the units ##STR1## in which R.sup.1 -R.sup.4 =R.sup.5 -Si ##STR2## in which R.sup.5 =alkylene with C.sub.1 -C.sub.10 directly bound to P or N, cycloalkylene with C.sub.5 -C.sub.8 or ##STR3## The ratio between the number of moles of units (II) and the number of moles of bound metal atoms is 1:1 to 1.000 to 1 and the ratio between units (I) and (II) is preferably 10:90 to 95:5 mole %.The polymeric complex compounds are present macroscopically as spherical particles with a diameter of 0.01. to 3.0 mm, a BET surface of >0 to 1000 m.sup.2 /g, a specific pore volume of 0.01 to 6.5 ml/g, and a bulk density of 50 to 1000 g/l.Several methods of preparing the substance of the invention with special posttreatment stages and the use of the polymeric metal complexes as catalysts in organic chemistry are disclosed.