Methods for preparing ruthenium carbene complex precursors and ruthenium carbene complexes
View Patent ↗A method for preparing a ruthenium carbene complex precursor includes reacting a ruthenium refinery salt with a hydrogen halide to form a ruthenium intermediate, and reacting the ruthenium intermediate with an L-type ligand to form the ruthenium carbene complex precursor. A method for preparing a ruthenium vinylcarbene complex includes converting a ruthenium carbene complex precursor into a ruthenium hydrido halide complex, and reacting the ruthenium hydrido halide complex with a propargyl halide to form the ruthenium vinylcarbene complex. A method for preparing a ruthenium carbene complex includes converting a ruthenium carbene complex precursor into a ruthenium carbene complex having a structure (PR 1 R 2 R 3 ) 2 Cl 2 Ru═CH—R 4 , wherein R 1 , R 2 , R 3 , and R 4 are alike or different, and wherein covalent bonds may optionally exist between two or more of R 1 , R 2 , and R 3 .
1. A method of preparing a MX 2 L q complex comprising:
reacting a ruthenium (IV) hexahalo complex that comprises a [RuX 1 y X 2 6−y ] 2− anion with an L-type ligand to form the MX 2 L q complex;
wherein M is ruthenium;
wherein X 1 and X 2 are halogen atoms that are independently selected from the group consisting of Cl and Br;
wherein X is a halogen atom selected from the group consisting of Cl and Br;
wherein y is an integer value from 1 to 6; and
wherein q is 3.
2. The method of claim 1 wherein the L-type ligand is selected from the group consisting of olefins, phosphines, phosphites, amines, CO, N 2 , and combinations thereof.
3. The method of claim 2 , wherein the L-type ligand is selected from the group consisting of olefins, phosphines, and combinations thereof.
4. The method of claim 1 , wherein the L-type ligand comprises a phosphine.
5. The method of claim 4 , wherein the L-type ligand comprises a phosphorous-containing ligand having a structure PR 1 R 2 R 3 ;
wherein R 1 , R 2 , and R 3 are alike or different and are each independently selected from the group consisting of substituted or unsubstituted aryl, substituted or unsubstituted C 1 -C 10 alkyl, substituted or unsubstituted aryloxy, substituted or unsubstituted C 1 -C 10 alkoxy, and combinations thereof; and
wherein covalent bonds may optionally exist between two or more of R 1 , R 2 , and R 3 , such that when two or more of R 1 , R 2 , and R 3 are taken together, a bidentate ligand to phosphorous is formed.
6. The method of claim 5 , wherein the phosphorous-containing ligand is triphenyl phosphine.
7. The method of claim 4 , further comprising replacing one or more L-type ligands of the MX 2 L q complex with an N-heterocyclic carbene ligand to form an N-heterocyclic carbene-containing ruthenium carbene complex.
8. The method of claim 4 , further comprising replacing a phosphorous-containing ligand of the MX 2 L q complex with an imidazolidine ligand to form an imidazolidine-containing ruthenium carbene complex.
9. The method of claim 5 , further comprising replacing one or more L-type ligands of the MX 2 L q complex with an N-heterocyclic carbene ligand to form an N-heterocyclic carbene-containing ruthenium carbene complex.
10. The method of claim 5 , further comprising replacing a phosphorous-containing ligand of the MX 2 L q complex with an imidazolidine ligand to form an imidazolidine-containing ruthenium carbene complex.
11. The method of claim 6 , further comprising replacing one or more L-type ligands of the MX 2 L q complex with an N-heterocyclic carbene ligand to form an N-heterocyclic carbene-containing ruthenium carbene complex.
12. The method of claim 6 , further comprising replacing a phosphorous-containing ligand of the MX 2 L q complex with an imidazolidine ligand to form an imidazolidine-containing ruthenium carbene complex.
13. The method of claim 1 , wherein the ruthenium (IV) hexahalo complex comprises a [RuCl 6 ] 2− anion.
14. The method of claim 4 , wherein the ruthenium (IV) hexahalo complex comprises a [RuCl 6 ] 2− anion.
15. The method of claim 1 , wherein the ruthenium (IV) hexahalo complex comprises one or more ammonium cations.
16. The method of claim 4 , wherein the ruthenium (IV) hexahalo complex comprises one or more ammonium cations.