Metallocene-Substituted Pyridyl Amines, Their Metal Complexes, and Processes for Production and Use Thereof

A transition metal complex represented by the formula:

• wherein
• M1 is a metal atom selected from the group consisting of Fe, Ru, and Co;
• Q is —CR3R4— or —SiR3R4—;
• Z is —NR1R2 or —NR2 and
• R1 to R16 are independently selected from the group consisting of hydrogen, alkyl, aryl, arylalkyl, halogen, alkoxy, aryloxy, amino, and silyl;
• and
• M2 is a group 3 through group 6 metal with one to four additional donor and/or anionic ligands coordinated to M2, and
• two adjacent carbon atoms of at least one cyclopentadienyl moiety may be linked by a saturated or unsaturated cyclic moiety having from 3 to 6 carbon atoms, optionally containing a heteroatom, and R1 and R2 in —NR1R2 and R3 and R4 in CR3R4— or —SiR3R4 may form a chain of from 3 to 6 carbon atoms, optionally including a heteroatom.

A process for producing a transition metal complex which comprises reacting a metallocenylboronic acid with a pyridyl compound containing at least one pyridyl-halogen or triflate group in the presence of a Pd catalyst and producing a metallocenyl pyridine compound represented by the Formula (I):

• wherein
• M1 is a metal atom selected from the group consisting of Fe, Ru, and Co;
• Y is a reactive moiety selected from the group consisting of —CHO, —C(O)R4 and a halogen, and
• R4 to R16 are independently selected from the group consisting of hydrogen, alkyl, aryl, arylalkyl, halogen, alkoxy, aryloxy, amino, and silyl, and two adjacent carbon atoms of at least one cyclopentadienyl moiety may be linked by a saturated or unsaturated cyclic moiety having from 3 to 6 carbon atoms, optionally containing a heteroatom, where the process comprises coupling a di-halo-pyridine or a halo-pyridine-aldehyde or halo-pyridine-ketyl species with a metallocenyl-based boronic acid to produce a compound in which —Y is halogen or —CHO or —C(O)R4 as represented by Formula (I), thereafter lithiating the compound represented by Formula (I) in which —Y is halogen and reacting the lithio product with a mono- or dichloro silicon derivative and, optionally, an amine or metal amido reagent, or reacting the compound represented by Formula (I) in which —Y is —CHO or —C(O)R4 with an amine and subsequently with an organometallic reagent to form a ligand precursor compound represented by Formula (II):
• wherein
• M1, and R4 to R16 are as defined for Formula I;
• Q is —CR3R4— or —SiR3R4—;
• Z is —NR1R2;
• and
• R1 to R3 are independently selected from the group consisting of hydrogen, alkyl, aryl, arylalkyl, halogen, alkoxy, aryloxy, amino, and silyl, and two adjacent carbon atoms of at least one cyclopentadienyl moiety may be linked by a saturated or unsaturated cyclic moiety having from 3 to 6 carbon atoms, optionally containing a heteroatom, and
• R1 and R2 in —NR1R2 and R3 and R4 in CR3R4— or —SiR3R4 may form a chain of from 3 to 6 carbon atoms, optionally including a heteroatom, and thereafter subjecting the amine derivative produced to a protonolysis reaction between the ligand precursor and an organometallic reagent and then, optionally, alkylating the product by transmetalation to produce a transition metal complex represented by the formula:
• wherein
• M1 is a metal atom selected from the group consisting of Fe, Ru, and Co;
• Q is —CR3R4— or —SiR3R4—;
• and
• R1 to R16 and Z are as defined form formula II, M2 is a group 3, 4, 5, or 6 metal with one to four additional donor and/or anionic ligands coordinated to M2, and two adjacent carbon atoms of at least one cyclopentadienyl moiety may be linked by a saturated or unsaturated cyclic moiety having from 3 to 6 carbon atoms, optionally containing a heteroatom.