Complexes of mid-transition metals and unsaturated nitrogenous ligands as single-site catalysts

A compound having the structure of formula (I)

• 27
• wherein:
• M is a mid-transition metal;
• Q1 and Q2 are independently selected from the group consisting of hydrido, halide, alkoxy, amido, unsubstituted C1-C30 hydrocarbyl, C1-C30 hydrocarbyl substituted with one or more substituents such as electron-withdrawing groups, and C1-C30 hydrocarbyl-substituted Group IVB elements, or Q1 and Q2 may together form an alkylidene olefin, acetylene, or a five- or six-membered cyclic hydrocarbyl group;
• m and n are independently zero or 1;
• q is an optional double bond;
• X is N, O, S or P, with the provisos that (a) when X is N or P, then either n is 1 or q is present as a double bond, but not both, and (b) when X is O or S, then n is zero and q is absent;
• R1, R6, and R7 are independently hydrido, hydrocarbyl or substituted hydrocarbyl, and R2 and R5 are independently hydrido, halo, hydrocarbyl or substituted hydrocarbyl, or R1 and R2 and/or R5 and R6 may be taken together to form a linkage —Q—, resulting in a five- or six-membered ring, wherein Q is —[(CR)a(Z)b]— in which a is 2, 3 or 4, Z is N, O or S, b is zero or 1, the sum of a and b is 3 or 4, and R is selected from the group consisting of hydrido, halo, hydrocarbyl, hydrocarbyloxy, trialkylsilyl, NR82, OR9, and NO2, wherein R8 and R9 are each independently hydrocarbyl, or wherein R moieties on adjacent carbon atoms may be linked to form an additional five- or six-membered ring, or R2 and R5 may together form a linkage —Q— as just defined;
• R3 and R4 are independently selected from the group consisting of hydrido and hydrocarbyl, or at least one of R3 and R4 may be bound through a lower alkylene linkage to an atom contained within LA or LB;
• LA and LB are ligands which may be the same or different and are independently selected from the group consisting of nitrogen-containing, sulfur-containing and oxygen-containing heterocycles, tertiary amines and phosphines, or LA and LB may together form a single bidentate ligand that may or may not be the same as L1,
• with the proviso that when (a) LA and LB form a single bidentate ligand that is identical to L1 and M is V or Cr, then either (b) R1 and R2 or R5 and R6 are taken together to form a linkage —Q— as defined above, or (c) X is other than N, or both (b) and (c).

A compound having the structure of formula (III)

• 30
• wherein:
• M is a mid-transition metal;
• Q1 and Q2 are independently selected from the group consisting of hydrido, halide, alkoxy, amido, unsubstituted C1-C30 hydrocarbyl, C1-C30 hydrocarbyl substituted with one or more substituents such as electron-withdrawing groups, and C1-C30 hydrocarbyl-substituted Group IVB elements, or Q1 and Q2 may together form an alkylidene olefin, acetylene, or a five- or six-membered cyclic hydrocarbyl group;
• LA and LB are ligands which may be the same or different and are independently selected from the group consisting of nitrogen-containing, sulfur-containing and oxygen-containing heterocycles, tertiary amines and phosphines, or LA and LB may together form a single bidentate ligand that may or may not be the same as L3;
• i and j are independently zero, 1, 2 or 3;
• and
• R10, R11, R12 and R13 are independently hydrido, hydrocarbyl or substituted hydrocarbyl.