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Catalytic composition effective in the hydrogenation of olefinic double bonds prepared by reaction between: (A) at least one cyclopentadienyl complex of a transi- tion metal having general formula (I) (R) (R1)M1(R2) (R3) wherein R is an anion containing an n5-cyclopentadienyl ring coordinated to M1; M1 is selected from titanium, zirconium and hafnium; R2 and R3, the same or different, are organic or inorganic anion groups bound to M1; R1 is selected from cyclopentadienyl and R2; (B) an alkylating composition essentially consisting of: (bI) an organometallic compound having general formula (II) M2 (R4)(R5) , wherein M2 is selected from Zn and Mg; (b2) an organoderivative of aluminum having general formula (III) Al(R6)3.