Synthesis of bis(azinyl)amine-BF2 complex

1. A process of forming a 2-2′ bis(pyridyl)amine-BF 2 complex, where a boron atom is complexed by two ring nitrogens, comprising the step of reacting BF 3 with an amine having Formula (1)

wherein:

A and A′ represent independent azine ring systems corresponding to 6-membered aromatic ring systems containing at least one nitrogen;

each X a and X b is an independently selected substituent, two of which may join to form a fused ring to A or A′;

m and n are independently 0 to 4; and

atoms 1, 2, 3, 4, 1′, 2′, 3′, and 4′ are carbon atoms;

in the presence of a polar aprotic organic solvent containing a nitrile group that is not reactive with the BF 3 under reaction conditions and has the Formula:

wherein

R 1 , R 2 and R 3 each independently resents hydrogen, fluorine, alkyl, aryl, alkoxy, aryloxy, dialkylamino, diarylamino, cyano, or nitro groups wherein at least one of R 1 , R 2 and R 3 is not H; and

R 1 and R 2 , R 2 and R 3 or R 1 and R 3 may join to form a cycloalkyl or an aryl ring group.

2. The process of claim 1 wherein at least two of R 1 , R 2 and R 3 are not H.

3. The process of claim 1 wherein R 1 and R 2 represent H and R 3 represents a methyl group.

4. The process of claim 1 wherein R 1 and R 2 represent H and R 3 represents an ethyl group.

5. The process of claim 1 wherein at least two of R 1 , R 2 and R 3 are H.

6. The process of claim 1 wherein the BF 3 source is selected from the group consisting of BF 3 gas, BF 3 solution in an organic solvent or BF 3 complex with organic solvent or compound.

7. The process of claim 1 wherein the BF 3 source is selected from the group consisting of BF 3 complexed with diethyl ether, dimethyl ether or tetrahydrofuran.

8. The process of claim 1 wherein BF 3 is used in the amount 1-50 equivalents per mol of the amine compound having Formula (1).

9. The process of claim 1 wherein the reaction is performed at a temperature of at least 18° C.

10. The process of claim 1 wherein the reaction is performed at a temperature of at least 80° C.

11. The process of claim 1 wherein the reaction is performed at a temperature of at least 115° C.

12. The process of claim 1 where at least one X a or X b is present containing 4 or more carbon atoms.

13. The process of claim 12 wherein the X a or X b group is selected from the group consisting of phenyl and t-butyl groups.

14. The process of claim 13 wherein the X a or X b group is a phenyl group.

15. The process of claim 13 wherein the X a or X b group is a phenyl group containing at least one methyl group substituent.

16. The process of claim 13 wherein the X a or X b group is a mesityl group.

17. The process of claim 1 wherein the amine-BF 2 complex is selected from the following: