Stereospecific metallocene catalysts with stereolocking .alpha.-CP substituents

A metallocene catalyst for preparing syndiospecific polyolefins comprising a catalyst or catalyst precursor characterized by formula (VI):

• ##STR15## where:
• A is a structural bridge selected from the group consisting of a C1-C20 alkenyl radical, a peralkylated C1-C20 alkenyl radical, a dialkyl methylene radical, a C3-C12 cyclohydrocarbyl radical, an aryl radical, a diarylmethylene radical, a diaryl allenyl radical, a silicon hydrocarbyl radical, a dihydrocarbyl silenyl radical, a germanium hydrocarbyl radical, a phosphorus hydrocarbyl radical, a nitrogen hydrocarbyl radical, a boron hydrocarbyl radical, and an aluminum hydrocarbyl radical;
• R.sup.19 and R.sup.20 are the same or different radicals and are a linear or branched C1-C20 hydrocarbyl radical, a linear or branched C1-C20 halocarbyl radical, a C1-C20 hydrohalocarbyl radical, a linear or branched C1-C20 alkoxy radical, a C3-C12 cyclohydrocarbyl radical, a C3-C12 cyclohydrohalocarbyl radical, an aryl radical, an alkylaryl radical, an arylalkyl radical, a silicon hydrocarbyl radical, a germanium hydrocarbyl radical, a phosphorus hydrocarbyl radical, a nitrogen hydrocarbyl radical, a boron hydrocarbyl radical, an aluminum hydrocarbyl radical, a C1 atom, a Br atom, or an I atom;
• R.sup.21 and R.sup.22 and R.sup.23 and R.sup.24 are the same or different radicals as described for R.sup.19 and R.sup.2 and R.sup.21 and R.sup.22 or R.sup.23 and R.sup.24 can be joined together into saturated, unsaturated or aromatic fused ring;
• Me is a Group 3, 4, or 5 metal, or Lu, La, Nd, or Sin;
• Q is a hydrocarbyl radical or halogen atom;
• P is a stable non-coordinating or pseudo-non-coordinating anion;
• k is an integer having a value from 0 to 2;
• l is an integer having a value from 0 to 2;
• and
• the overall catalyst has C.sub.s or pseudo-C.sub.s symmetry.

A metallocene catalyst for preparing syndiospecific polyolefins comprising a catalyst or catalyst precursor characterized by formula (VII):

• ##STR16## where:
• A is a structural bridge selected from the group consisting of a C1-C20 alkenyl radical, a peralkylated C1-C20 alkenyl radical, a dialkyl methylene radical, a C3-C12 cyelohydroeaxbyl radical, an aryl radical, a diarylmethylene radical, a diaryl allenyl radical, a silicon hydroearbyl radical, a dihydrocarbyl silenyl radical, a germanium hydrocarbyl radical, a phosphorus hydrocarbyl radical, a nitrogen hydrocarbyl radical, a boron hydrocarbyl radical, and an aluminum hydrocarbyl radical;
• R.sup.25 and R.sup.26 are the same or different radicals and are a linear or branched C1-C20 hydrocarbyl radical, a linear or branched C1-C20 halocarbyl radical, a C1-C20 hydrohalocarbyl radical, a linear or branched C1-C20 alkoxy radical, a C3-C12 cyclohydrocarbyl radical, a C3-C12 cyclohydrohalocarbyl radical, an aryl radical, an alkylaryl radical, an arylalkyl radical, a silicon hydrocarbyl radical, a germanium hydrocarbyl radical, a phosphorus hydrocarbyl radical, a nitrogen hydrocarbyl radical, a boron hydrocarbyl radical, an aluminum hydrocarbyl radical, a Cl atom, a Br atom, or an I atom;
• R.sup.27 and R.sup.28 are the same or different and are a hydrogen atom or a radical as described for R.sup.25 and R.sup.26 ;
• Me is a Group 3, 4, or 5 metal, or Lu, La, Nd, or Sin;
• Q is a hydrocarbyl radical or halogen atom;
• P is a stable non-coordinating or pseudo-non-coordinating anion;
• k is an integer having a value from 0 to 2;
• l is an integer having a value from 0 to 2;
• and
• the overall catalyst has C.sub.s or pseudo-C.sub.s symmetry.

A metallocene catalyst or catalyst precursor for preparing syndiospecific polyolefins comprising a metallocene characterized by formula (I):

• ##STR17## where:
• A is a structural bridge selected from the group consisting of a C1-C20 alkenyl radical, a peralkylated C1-C20 alkenyl radical, a dialkyl methylene radical, a C3-C12 cyclohydrocarbyl radical, an aryl radical, a diarylmethylene radical, a diaryl allenyl radical, a silicon hydrocarbyl radical, a dihydrocarbyl silenyl radical, a germanium hydrocarbyl radical, a phosphorus hydrocarbyl radical, a nitrogen hydrocarbyl radical, a boron hydrocarbyl radical, and an aluminum hydrocarbyl radical;
• Z is a cyclopentadienyl radical having a 2,5 substitution pattern where the 2,5 substituents on the Z radical are a linear or branched C1-C20 hydrocarbyl radical, a linear or branched C1-C20 halocarbyl radical, a C1-C20 hydrohalocarbyl radical, a linear or branched C1-C20 alkoxy radical, a C3-C12 cyclohydrocarbyl radical, a C3-C12 cyclohydrohalocarbyl radical, an aryl radical, an alkylaryl radical, an arylalkyl radical, a silicon hydrocarbyl radical, a germanium hydrocarbyl radical, a phosphorus hydrocarbyl radical, a nitrogen hydrocarbyl radical, a boron hydrocarbyl radical, an aluminum hydrocarbyl radical, a Cl atom, a Br atom, or an I atom;
• Z' is a fluorenyl radical;
• Me is a Group 3, 4, or 5 metal or Lu, La, Nd, or Sm;
• Q is a hydrocarbyl radical or halogen atom;
• P is a stable non-coordinating or pseudo-non-coordinating anion;
• k is an integer having a value from 0 to 2;
• l is an integer having a value from 0 to 2;
• and
• the overall catalyst has C.sub.s or pseudo-C.sub.s symmetry.

A metallocene catalyst or catalyst precursor for preparing syndiospecific polyolefins comprising a metallocene characterized by formula (I):

• ##STR18## where:
• A is a structural bridge selected from the group consisting of a C1-C20 alkenyl radical, a peralkylated C1-C20 alkenyl radical, a dialkyl methylene radical, a C3-C 12 cyclohydrocarbyl radical, an aryl radical, a diarylmethylene radical, a diaryl allenyl radical, a silicon hydrocarbyl radical, a dihydrocarbyl silenyl radical, a germanium hydrocarbyl radical, a phosphorus hydrocarbyl radical, a nitrogen hydrocarbyl radical, a boron hydrocarbyl radical, and an aluminum hydrocarbyl radical;
• Z is a cyclopentadienyl radical where the 2 and 5 positions of the Cp ring bear substituents sterically larger than a hydrogen atom and Z' is a cyclopentadienyl radical where at least the 3 and 4 positions of the Cp ring bear substituents sterically larger than a hydrogen atom and where the 3,4 substituents can be part of a saturated or unsaturated fused ring and where the 2,5 substituents on Z and the 3,4 substituents on Z' are a linear or branched C 1-C20 hydrocarbyl radical, a linear or branched C1-C20 halocarbyl radical, a C1-C20 hydrohalocarbyl radical, a linear or branched C1-C20 alkoxy radical, a C3-C12 cyclohydrocarbyl radical, a C3 -C 12 cyclohydrohalocarbyl radical, an aryl radical, an alkylaryl radical, an arylalkyl radical, a silicon hydrocarbyl radical, a germanium hydrocarbyl radical, a phosphorus hydrocarbyl radical, a nitrogen hydrocarbyl radical, a boron hydrocarbyl radical, an aluminum hydrocarbyl radical, a Cl atom, a Br atom, or an I atom;
• Me is a Group 3, 4, or 5 metal, or Lu, La, Nd, or Sm;
• Q is a hydrocarbyl radical or halogen atom;
• P is a stable non-coordinating or pseudo-non-coordinating anion;
• k is an integer having a value from 0 to 2;
• l is an integer having a value from 0 to 2;
• and
• the overall catalyst has C.sub.s or pseudo-C.sub.s symmetry.