Catalyst systems for olefin polymerization

A catalyst system comprising the reaction product of a metal-ligand complex of formula (I):

• wherein:
• M is titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3, or +4;
• and n is an integer of from 0 to 3, and wherein when n is 0, X is absent;
• and each X independently is a monodentate ligand that is neutral, monoanionic, or dianionic;
• or two Xs are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic;
• and X and n are chosen in such a way that the metal-ligand complex of formula (I) is, overall, neutral;
• and each Z independently is O, S, N(C1-C40)hydrocarbyl, or P(C1-C40)hydrocarbyl;
• and L is (C3-C40)hydrocarbylene or (C3-C40)heterohydrocarbylene, wherein the (C3-C40)hydrocarbylene has a portion that comprises a 3-carbon atom to 10-carbon atom linker backbone linking the Z atoms in formula (I) (to which L is bonded) and the (C3-C40)heterohydrocarbylene has a portion that comprises a 3-atom to 10-atom linker backbone linking the Z atoms in formula (I), wherein each of the 3 to 10 atoms of the 3-atom to 10-atom linker backbone of the (C3-C40)heterohydrocarbylene independently is a carbon atom or heteroatom, wherein each heteroatom independently is O, S, S(O), S(O)2, Si(RC)2, Ge(RC)2, P(RP), or N(RN), wherein independently each RC is (C1-C30)hydrocarbyl, each RP is (C1-C30)hydrocarbyl;
• and each RN is (C1-C30)hydrocarbyl or absent;
• and
• R1-24 are selected from the group consisting of a (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, Si(RC)3, Ge(RC)3, P(RP)2, N(RN)2, ORC, SRC, NO2, CN, CF3, RCS(O)—, RCS(O)2—, (RC)2C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(R)—, (RC)2NC(O)—, halogen atom, hydrogen atom, and combination thereof;
• and, wherein at least R1, R16, or both comprise of formula (II),
• wherein at least one of R22 or R19 is H, and when R22 is H, then R19 is a (C1-C40)hydrocarbyl;
• (C1-C40)heterohydrocarbyl;
• Si(RC)3, Ge(RC)3, P(RP)2, N(RN)2, ORC, SRC, NO2, CN, CF3, RCS(O)—, RCS(O)2—, (RC)2C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(R)—, (RC)2NC(O)— or halogen atom;
• and when R19 is H, then R22 is a (C1-C40)hydrocarbyl;
• (C1-C40)heterohydrocarbyl;
• Si(RC)3, Ge(RC)3, P(RP)2, N(RN)2, ORC, SRC, NO2, CN, CF3, RCS(O)—, RCS(O)2—, (RC)2C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(R)—, (RC)2NC(O)— or halogen atom;
• and
• wherein at least one of R8 or R9 is H, and when R8 is H, then R9 is a (C1-C40)hydrocarbyl;
• (C1-C40)heterohydrocarbyl, Si(RC)3, Ge(RC)3, P(RP)2, N(RN)2, ORC, SRC, NO2, CN, CF3, RCS(O)—, RCS(O)2—, (RC)2C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(R)—, (RC)2NC(O)— or halogen atom;
• and when R9 is H, then R8 is a (C1-C40)hydrocarbyl;
• (C1-C40)heterohydrocarbyl, Si(RC)3, Ge(RC)3, P(RP)2, N(RN)2, ORC, SRC, NO2, CN, CF3, RCS(O)—, RCS(O)2—, (RC)2C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(R)—, (RC)2NC(O)— or halogen atom;
• and
• optionally two or more R groups from R9-15, R9-13, R9-12, R2-8, R4-8, R5-8 can combine together into ring structures, with such ring structures having from 3 to 50 atoms in the ring excluding any hydrogen atoms;
• each of the hydrocarbyl, heterohydrocarbyl, Si(RC)3, Ge(RC)3, P(RP)2, N(RN)2, ORC, SRC, RCS(O)—, RCS(O)2—, (RC)2C═N—, RCC(O)O—, RCOC(O)—, RCC(O)N(R)—, (RC)2NC(O)—, hydrocarbylene, and heterohydrocarbylene groups independently is unsubstituted or substituted with one or more RS substituents;
• each RS independently is a halogen atom, polyfluoro substitution, perfluoro substitution, unsubstituted (C1-C18)alkyl, F3C—, FCH2O—, F2HCO—, F3CO—, R3Si—, R3Ge—, RO—, RS—, RS(O)—, RS(O)2—, R2P—, R2N—, R2C═N—, NC—, RC(O)O—, ROC(O)—, RC(O)N(R)—, or R2NC(O)—, or two of the RS are taken together to form an unsubstituted (C1-C18)alkylene, wherein each R independently is an unsubstituted (C1-C18)alkyl;
• and
• one or more cocatalysts;
• wherein the ratio of total number of moles of the one or more metal-ligand complexes of formula (I) to total number of moles of the one or more cocatalysts is from 1:10,000 to 100:1;
• and
• wherein said catalyst system has a reactivity ratio r1 in the range of greater than 100.