Methods for preparing ruthenium carbene complex precursors and ruthenium vinylcarbene complexes

A method for preparing a ruthenium carbene complex precursor comprising:

• reacting a ruthenium refinery salt with a hydrogen halide to form a ruthenium intermediate;
• and
• reacting the ruthenium intermediate with cyclooctadiene and/or a phosphorous-containing material having a structure PR1R2R3 to form the ruthenium carbene complex precursor;
• wherein the ruthenium refinery salt comprises a material selected from the group consisting of (NH4)2RuCl5, (NH4)2RuCl5.H2O, polyhydrated (NH4)2RuCl5, (NH4)4[Ru2OCl10], and combinations thereof;
• wherein the ruthenium intermediate comprises a compound selected from the group consisting of (NH4)2RuX16, (NH4)2RuX1yX26-y, and a combination thereof;
• wherein the ruthenium carbene complex precursor comprises a compound having a structure [RuX3X4(COD)]x and/or a compound having a structure RuX5X6(PR1R2R3)3;
• wherein x is an integer value of 1 or more;
• wherein X1, X2, X3, X4, X5, and X6 are halogen atoms that are each independently selected from the group consisting of F, Cl, Br, and I with a caveat that X1 and X2 are different;
• wherein y is an integer value from 1 to 5;
• wherein R1, R2, and R3 are alike or different and are each independently selected from the group consisting of substituted or unsubstituted aryl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted aryloxy, substituted or unsubstituted C1-C10 alkoxy, and combinations thereof;
• and
• wherein covalent bonds may optionally exist between two or more of R1, R2, and R3, such that when two or more of R1, R2, and R3 are taken together, a bidentate ligand to phosphorous is formed.

A method of preparing a MX2Lq complex comprising:

• reacting a ruthenium (IV) hexahalo complex that comprises a [RuX1yX26-y]2− anion with an L-type ligand;
• wherein M comprises ruthenium;
• wherein X1 and X2 are halogen atoms that are independently selected from the group consisting of F, Cl, Br, and I;
• and
• wherein y is an integer value from 1 to 6.