Synthesis of aryl coupled bis phenoxides and their use in olefin polymerization catalyst systems with activator-supports

1. A method of making a transition metal bis(phenolate) compound having the formula:

the method comprising:

(i) contacting a phenol compound having the formula:

 with

(a) zinc metal;

(b) a zinc-containing transfer agent; or

(c) a halogen transfer agent and a zinc transfer compound;

in the presence of a reaction solvent to form a first mixture;

(ii) contacting the first mixture with a palladium cross-coupling catalyst system and a substituted or unsubstituted, saturated or unsaturated, C 4 to C 8 heterocyclic compound having the formula:

to form a ligand reaction mixture comprising a bis(phenol) ligand compound having formula (II):

 and

(iii) contacting the ligand compound having formula (II) with M(X)(X)(X)(X), optionally in the presence of a second solvent, to form a transition metal compound reaction mixture comprising the transition metal bis(phenol) compound having formula (I); wherein:

R 2 , R 3 , R 4 , and R 5 independently are H or a C 1 to C 18 hydrocarbyl or halogenated hydrocarbyl group;

 is a substituted or unsubstituted, saturated or unsaturated, C 4 to C 8 heterocyclic group, wherein each R A independently is a C 1 to C 18 hydrocarbyl or halogenated hydrocarbyl group, and m is 0, 1, 2, or 3;

each X A independently is Cl, Br, or I;

M is Ti, Zr, or Hf;

each X independently is a monoanionic ligand; and

each L independently is a neutral ligand, wherein n is 0, 1 or 2.

2. The method of claim 1 , wherein M is Zr and each X is benzyl.

3. The method of claim 1 , wherein each L is independently an ether, an organic carbonyl, a thioether, an amine, a nitrile, or a phosphine.

4. The method of claim 1 , wherein each L is independently dimethyl ether, diethyl ether, tetrahydrofuran, furan, benzofuran, tetrahydropyran, 1,4-dioxane, or morpholine.

5. The method of claim 1 , wherein L is diethyl ether and n is 1.

6. The method of claim 1 , wherein:

R 2 , R 3 , R 4 , and R 5 independently are H or a C 1 to C 6 alkyl group;

each R A independently is a C 1 to C 8 hydrocarbyl group;

m is 0, 1, or 2; and

each X A independently is Br or I.

7. The method of claim 6 , wherein:

R 2 and R 4 independently are a C 1 to C 6 alkyl group, and R 3 and R 5 are H;

 and

each X A is Br.

8. The method of claim 1 , wherein the phenol compound having the formula (III) is contacted with zinc metal and an alkali metal salt and/or alkaline earth metal salt.

9. The method of claim 1 , wherein the phenol compound having the formula (III) is contacted with the zinc-containing transfer agent.

10. The method of claim 1 , wherein the phenol compound having the formula (III) is contacted with:

dimethyl zinc, diethyl zinc, or a combination thereof; and

LiCl, MeLi, NaCl, KCl, NaBr, MgBr 2 , MgCl 2 , or a combination thereof.

11. l The method of claim 1 , wherein:

the phenol compound having the formula (III) is contacted with the halogen transfer agent and the zinc transfer compound;

the halogen transfer agent comprises lithium metal, sodium metal, potassium metal, magnesium metal, a hydrocarbyl lithium compound, a hydrocarbyl sodium compound, a hydrocarbyl potassium compound, a hydrocarbyl magnesium compound, or a combination thereof; and

the zinc transfer compound has the formula, Zn(X)(X) (IV);

wherein each X in formula (IV) independently is a monoanionic ligand.

12. The method of claim 1 , wherein the palladium cross-coupling catalyst system comprises Pd(OAc) 2 , PdCl 2 , Pd 2 (dba) 3 , Pd(dba) 2 , Pd(PPh 3 ) 4 , Pd/C, (MeCN) 2 PdCl 2 , or any combination thereof.

13. A method of making a bis(phenol) ligand compound having the formula:

the method comprising:

(i) contacting a phenol compound having the formula:

 with

(a) zinc metal;

(b) a zinc-containing transfer agent; or

(c) a halogen transfer agent and a zinc transfer compound; in the presence of a reaction solvent to form a first mixture; and

(ii) contacting the first mixture with a palladium cross-coupling catalyst system and a substituted or unsubstituted, saturated or unsaturated, C 4 to C 8 heterocyclic compound having the formula:

to form a ligand reaction mixture comprising the bis(phenol) ligand compound having formula (II); wherein:

R 2 , R 3 , R 4 , and R 5 independently are H or a C 1 to C 18 hydrocarbyl or halogenated hydrocarbyl group;

 is a substituted or unsubstituted, saturated or unsaturated, C 4 to C 8 heterocyclic group, wherein each R A independently is a C 1 to C 18 hydrocarbyl or halogenated hydrocarbyl group, and m is 0, 1, 2, or 3; and

each X A independently is Cl, Br, or I.

14. The method of claim 13 , wherein:

R 2 , R 3 , R 4 , and R 5 independently are H or a C 1 to C 6 alkyl group;

each R A independently is a C i to C 8 hydrocarbyl group;

m is 0, 1, or 2; and

each X A independently is Br or I.

15. The method of claim 14 , wherein:

R 2 and R 4 independently are a C 1 to C 6 alkyl group, and R 3 and R 5 are H;

 and

each X A is Br.

16. The method of claim 3 , wherein

17. The method of claim 13 , wherein the phenol compound having the formula (III) is contacted with zinc metal and an alkali metal salt and/or alkaline earth metal salt.

18. The method of claim 13 , wherein the phenol compound having the formula (III) is contacted with the zinc-containing transfer agent.

19. The method of claim 13 , wherein the phenol compound having the formula (III) is contacted with:

dimethyl zinc, diethyl zinc, or a combination thereof; and

LiCl, MeLi, NaCl, KCl, NaBr, MgBr 2 , MgCl 2 , or a combination thereof.

20. The method of claim 13 , wherein the phenol compound having the formula (III) is contacted with the halogen transfer agent prior to the zinc transfer compound.

21. The method of claim 13 , wherein:

the halogen transfer agent comprises lithium metal, sodium metal, potassium metal, magnesium metal, a hydrocarbyl lithium compound, a hydrocarbyl sodium compound, a hydrocarbyl potassium compound, a hydrocarbyl magnesium compound, or a combination thereof; and

the zinc transfer compound has the formula, Zn(X)(X) (IV);

wherein each X in formula (IV) independently is a monoanionic ligand.

22. The method of claim 13 , wherein:

the phenol compound having the formula (III) is contacted with the halogen transfer agent and the zinc transfer compound;

the halogen transfer agent comprises MeLi, n-BuLi, t-BuLi, n-hexylLi, LiCH 2 SiMe 3 , LiCH 2 Ph, LiCH 2 CMe 3 , PrMgCl, PhMgCl, EtMgBr, mesitylmagnesium bromide, Bu 3 MgLi, i-PrBu 2 MgLi, or any combination thereof; and

the zinc transfer compound comprises ZnCl 2 .

23. The method of claim 13 , wherein the reaction solvent comprises an ether solvent.

24. The method of claim 1 , wherein:

the phenol compound having the formula (III) is contacted with the halogen transfer agent and the zinc transfer compound;

the halogen transfer agent comprises n-BuLi; and

the zinc transfer compound comprises ZnCl 2 .

25. The method of claim 13 , wherein the palladium cross-coupling catalyst system comprises Pd(OAc) 2 , PdCl 2 , Pd 2 (dba) 3 , Pd(dba) 2 , Pd(PPh 3 ) 4 , Pd/C, (MeCN) 2 PdCl 2 , or any combination thereof.

26. The method of claim 25 , wherein the palladium cross-coupling catalyst system further comprises a phosphorus compound and/or a N-heterocyclic carbene compound.