A new class of heterocyclic metallocenes, a catalytic system containing them and a process for polymerizing addition polymerizable monomers using the catalytic system are disclosed; the heterocyclic metallocenes correspond to the formula (I): YjR″iZjjMeQkPl wherein Y is a coordinating group containing a six π electron central radical directly coordinating Me, to which are associated one or more radicals containing at least one non-carbon atom selected from B, N, O, Al, Si, P, S, Ga, Ge, As, Se, In, Sn, Sb and Te; R″ is a divalent bridge between the Y and Z groups; Z is a coordinating group, optionally being equal to Y; Me is a transition metal; Q is halogen or hydrocarbon substituents; P is a counterion; i is 0 or 1; j is 1-3; jj is 0-2; k is 1-3; and l is 0-2.