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It was shown that Pd(PtBu3)2 catalyzes cross-coupling reactions of halogen-substituted ansa-zirconocenes with MeZnCl, various aryl- and heteroarylzinc reagents. On the evidence of NMR spectroscopy, these reactions with bromo-substituted complexes proceed even at room temperature to form the target zirconocenes bearing methyl-, aryl-, and heteroaryl-substituted ligands in high or almost quantitative yield. Similar substitution of chlorine atom in the ligands proceeds at elevated temperature. Neither exchange of Cl ligands at Zr by Br nor epimerization process were observed under the conditions studied.