Process for the production of monohalide or dihalide metallocene compounds

A process for preparing dihalide or monohalide metallocene compounds of formula (I),

• (Cp)(ZR1m)n(A)rMLqL′s (I)
• wherein (ZR1m)n is a divalent group bridging Cp and A;
• Z being C, Si, Ge, N or P, and the R1 groups, equal to or different from each other, being hydrogen or linear or branched, saturated or unsaturated C1–C20 alkyl, C3–C20 cycloalkyl, C6–C20 aryl, C7–C20 alkylaryl or C7–C20 arylalkyl groups, optionally containing one or more heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements or two R1 can form a aliphatic or aromatic C4–C7 ring that can bear substituents;
• Cp is a substituted or unsubstituted cyclopentadienyl group, optionally condensed to one or more substituted or unsubstituted, saturated, unsaturated or aromatic rings, containing from 4 to 6 carbon atoms, optionally containing one or more heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements;
• A is O, S, NR2, PR2, wherein R2 is hydrogen, a linear or branched, saturated or unsaturated C1–C20 alkyl, C3–C20 cycloalkyl, C6–C20 aryl, C7–C20 alkylaryl or C7–C20 arylalkyl, or a substituted or unsubstituted cyclopentadienyl group, optionally condensed to one or more substituted or unsubstituted, saturated, unsaturated or aromatic rings, containing from 4 to 6 carbon atoms, optionally containing one or more heteroatoms belonging to groups 13–17 of the Periodic Table of the Elements;
• M is selected from zirconium, titanium or hafnium;
• L, equal to or different from each other, are selected from the group consisting of chlorine, bromine, and iodine;
• L′ is selected from the group consisting of hydrogen, a linear or branched, saturated or unsaturated C1–C20 alkyl, C3–C20 cycloalkyl, C6–C20 aryl, C7–C20 alkylaryl and C7–C20 arylalkyl group, optionally containing at least one Si or Ge atoms;
• m is 1 when Z is N or P, and m is 2 when Z is C, Si or Ge;
• n is 0, 1, 2, 3 or 4, being 0 when r is 0 or 2;
• r is 0, 1 or 2;
• q is 1, 2, or 3;
• s is 0 or 1;
• wherein q+s=3−r;
• said process comprising contacting a compound of formula (II)
• (Cp)(ZR1m)n(A)rML′y (II)
• wherein
• y is equal to s+q;
• with an halogenating agent selected from the group consisting of T1Lw1, T2Lw2, O=T3Lw3, and R6C(O)L, mercury dichloride (HgCl2) being excluded, wherein T1 is a metal of groups 3–13 of the Periodic Table of Elements or of the lanthanides series;
• T2 is a nonmetal element of groups 13–16 of the Periodic Table of Elements with the exclusion of carbon;
• T3 is selected from the group consisting of C, P and S;
• O is an oxygen atom bonded to T3 through a double bond;
• R6 is selected from a linear or branched, saturated or unsaturated C1–C20 alkyl, C3–C20 cycloalkyl, C6–C20 aryl, C7–C20 alkylaryl or C7–C20 arylalkyl;
• H is hydrogen;
• w1 is equal to the oxidation state of the metal T1;
• w2 is equal to the oxidation state of the element T2;
• w3 is equal to the oxidation state of the element T3 minus 2.