Ligands and catalyst systems thereof for ethylene oligomerisation to linear alpha olefins

A bis-imine pyridine ligand of formula (II):

• 30
• wherein A1-A6 are each, independently, carbon, nitrogen, oxygen, or sulphur;
• the atom group
• 31
• may be optionally absent such that A1 is directly bonded to A5;
• and R1-R12, R14-R15 and, if present, R13, are each, independently, hydrogen, optionally substituted hydrocarbyl, an inert functional group, or any two of R1-R15 vicinal to one another taken together may form a ring;
• with the proviso that when A1-A5, and A6 if present, are all carbon, said atoms constitute the cyclopentadienyl or aryl part of a π-co-ordinated metal.

A mixed bis-imine pyridine MXn complex comprising a ligand wherein M is a metal atom selected from Fe or Co, n is 2 or 3, and X is halide, optionally substituted hydrocarbyl, alkoxide, amide, or hydride, wherein said ligand is a mixed bis-imine pyridine ligand of formula (I):

• 32
• wherein R1-R5 are each, independently, hydrogen, optionally substituted hydrocarbyl, an inert functional group, or any two of R1-R3 vicinal to one another taken together may form a ring;
• Z1, which is different from Z2, is an optionally substituted aryl group;
• and Z2 is a heterohydrocarbyl group containing an optionally substituted heterohydrocarbyl moiety, or an optionally substituted aryl group in combination with a metal, said optionally substituted aryl group being π-co-ordinated to the metal.

The mixed bis-imine pyridine MXn complex comprising a ligand wherein M is a metal atom selected from Fe or Co, n is 2 or 3, and X is halide, optionally substituted hydrocarbyl, alkoxide, amide, or hydride, wherein said ligand is a bis-imide pyridine ligand of formula (II):

• 33
• wherein A1-A6 are each, independently, carbon, nitrogen, oxygen, or sulphur;
• the atom group
• 34
• may be optionally absent such that A1 is directly bonded to A5;
• and R1-R12, R14-R15 and, if present, R13, are each, independently, hydrogen, optionally substituted hydrocarbyl, an inert functional group, or any two of R1-R15 vicinal to one another taken together may form a ring;
• with the proviso that when A1-A5, and A6 if present, are all carbon, said atoms constitute the cyclopentadienyl or aryl part of a π-co-ordinated metal.

A mixed [bis-imine pyridine MYp.Ln+] [NC−]q complex comprising a mixed bis-imine pyridine ligand, wherein Y is a ligand which may insert an olefin;

• M is a metal atom selected from Fe or Co, NC− is a non-coordinating anion and p+q is 2 or 3, matching the formal oxidation state of said metal atom;
• L is a neutral Lewis donor molecule;
• and n=0, 1, or 2;
• wherein said mixed bis-imine pyridine ligand is a mixed bis-imine ligand of formula (I):
• 35
• wherein R1-R5 are each, independently, hydrogen, optionally substituted hydrocarbyl, an inert functional group, or any two of R1-R3 vicinal to one another taken together may form a ring;
• Z1, which is different from Z2, is an optionally substituted aryl group;
• and Z2 is a heterohydrocarbyl group containing an optionally substituted heterohydrocarbyl moiety, or an optionally substituted aryl group in combination with a metal, said optionally substituted aryl group being π-co-ordinated to the metal.

The mixed [bis-imine pyridine MYp.Ln+] [NC−]q complex comprising a mixed bis-imide pyridine ligand wherein Y is a ligand which may insert an olefin;

• M is a metal atom selected from Fe or Co, NC− is a non-coordinating anion and p+q is 2 or 3, matching the formal oxidation state of said metal atom;
• L is a neutral Lewis donor molecule;
• and n=0, 1, or 2;
• wherein said mixed bis-imide pyridine ligand is a bis-imide pyridine ligand of formula (II):
• 36
• wherein A1-A6 are each, independently, carbon, nitrogen, oxygen, or sulphur;
• the atom group
• 37
• may be optionally absent such that A1 is directly bonded to A5;
• and R1-R12, R14-R15 and, if present, R13, are each, independently, hydrogen, optionally substituted hydrocarbyl, an inert functional group, or any two of R1-R15 vicinal to one another taken together may form a ring;
• with the proviso that when A1-A5, and A6 if present, are all carbon, said atoms constitute the cyclopentadienyl or aryl part of a π-co-ordinated metal.