Bis-phenyl-phenoxy polyolefin catalysts having an alkoxy- or amido-ligand on the metal for improved solubility

1. A catalyst system comprising a metal-ligand complex according to formula (I):

where:

M is a metal chosen from titanium, zirconium, or hafnium, the metal being in a formal oxidation state of +2, +3, or +4;

X is selected from the group consisting of —OR X or —NR X 2 ; wherein each R X is independently a (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )heterohydrocarbyl, or —H and at least one R X is (C 1 -C 50 )hydrocarbyl, (C 1 -C 50 )heterohydrocarbyl, and, when X is —NR X 2 , optionally two R X are covalently linked;

the metal-ligand complex is overall charge-neutral;

each Z is independently chosen from —O—, —S—, —N(R N )—, or —P(R P )—;

R 1 and R 16 are independently selected from the group consisting of —H, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R P ) 2 , —N(R N ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 3 , R C S(O) 2 —, R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)—, halogen, radicals having formula (II), radicals having formula (III), and radicals having formula (IV):

where each of R 31-35 , R 41-48 , and R 51-59 is independently chosen from —H, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R P ) 2 , —N(R N ) 2 , —N═CHR C , —OR C , —SR C , —NO 2 , —CN, —CF 3 , R C S(O)—, R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R N )—, (R C ) 2 NC(O)—, or halogen,

provided that at least one of R 1 or R 16 is a radical having formula (II), a radical having formula (III), or a radical having formula (IV);

each of R 2-4 , R 5-8 , R 9-12 , and R 13-15 is independently selected from —H, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R P ) 2 , —N(R N ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 3 , R C S(O)—, R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)—, and halogen;

L is (C 2 -C 40 )hydrocarbylene or (C 2 -C 40 )heterohydrocarbylene; and

each R C , R P , and R N in formula (I) is independently a (C 1 -C 30 )hydrocarbyl, (C 1 -C 30 )heterohydrocarbyl, or —H.

2. The catalyst system according to claim 1 , wherein R X is chosen from (C 5 -C 50 )alkyl or —H.

3. The catalyst system according to claim 1 , wherein R X is linear.

4. The catalyst system according to claim 1 , wherein R X is branched.

5. The catalyst system according to claim 1 , wherein X is chosen from —OC x H 2x+1 and —NHC x H 2x+1 , where C x H 2x+1 is a linear alkyl and x is an integer from 10 to 40.

6. The catalyst system according to claim 1 , wherein:

M is zirconium or hafnium;

each X is —OC 22 H 45 ; and

each Z is oxygen.

7. The catalyst system according to claim 1 , wherein

M is zirconium or hafnium;

each X is —OC 18 H 37 ; and

each Z is oxygen.

8. The catalyst system according to claim 1 , wherein

M is zirconium or hafnium;

each X is —N(C 18 H 37 )R X ; and

each Z is oxygen.

9. The catalyst system according to claim 1 , wherein

M is zirconium or hafnium;

at least one X is —N(C 22 H 45 ) 2 ; and

each Z is oxygen.

10. The catalyst system according to claim 1 , wherein the metal-ligand complex according to formula (I) has a wt % solubility ratio W/Y of at least 1.5, wherein W is the wt % solubility of the metal-ligand complex of formula (I) in methylcyclohexane (MCH) at standard temperature and pressure (STP); wherein Y is the wt % solubility of a corresponding comparative metal-ligand complex of formula (Ia) in MCH at STP; and wherein the corresponding comparative complex has a structure according to formula (Ia):

in which M, each Z, each R 1-16 , and L, all are identical to corresponding groups of the metal-ligand complex according to formula (I).