Catalyst complex with carbene ligand

A catalytic complex of the formula:

• wherein either or both of C1 and C2 are optionally absent;
• M is selected from the group consisting of Os and Ru;
• R and R1 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C2-C20 alkoxycarbonyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy aryloxy, C1-C20 alkylthio, C1-C20 alkylsulfonyl, and C1-C20 alkylsulfinyl, each R and R1 optionally being substituted with C1-C5 alkyl, halogen, C1-C10 alkoxy, or with a phenyl group substituted with halogen, C1-C5 alkyl or C1-C5 alkoxy, or with a functional group;
• X is an anionic ligand;
• L is a nucleophilic carbene;
• Ar is an aryl substituent, bonded to M by an η6 bond;
• and
• A− is an inorganic anion or an organic anion.

A method of making a nucleophilic carbene, said method comprising:

• a) contacting a substituted or unsubstituted aniline with an approximately one-half equimolar amount of paraformaldehyde under an inert atmosphere to make a first reaction mixture;
• b) heating said first reaction mixture until said paraformaldehyde dissolves;
• c) adding an approximately one-half equimolar amount of a dialkoxyacetaldehyde to make a second reaction mixture;
• and
• d) heating said second reaction mixture for a time and under conditions sufficient to make a nucleophilic carbene.

A method of performing ring closing metathesis, said method comprising contacting a diene with a catalytic complex under conditions appropriate, and for a time sufficient to produce a cyclic alkene, wherein the catalytic complex has the formula:

• wherein M is Os or Ru;
• wherein C2 is optionally absent;
• R and R1 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C2-C20 alkoxycarbonyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C1-C20 alkylthio, C1-C20 alkylsulfonyl, and C1-C20 alkylsulfinyl, each R and R′ optionally being substituted with C1-C5 alkyl, halogen, C1-C10 alkoxy, or with a phenyl group substituted with halogen, C1-C5 alkyl or C1-C5 alkoxy, or with a functional group;
• X and X1 are independently selected from the group consisting of anionic ligands;
• L is selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, ether, amine, amide, sulfoxide, carbonyl, nitrosyl, pyridine and thioether;
• and
• L1 is a nucleophilic carbene.

A method of performing ring closing metathesis, said method comprising contacting a diene with a catalytic complex under conditions appropriate, and for a time sufficient to produce a cyclic alkene, wherein the catalytic complex has the formula:

• wherein either or both of C1 and C2 are optionally absent;
• M is selected from the group consisting of Os and Ru;
• R and R1 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C2-C20 alkoxycarbonyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C1-C20 alkylthio, C1-C20 alkylsulfonyl, and C1-C20 alkylsulfinyl, each R and R1 optionally being substituted with C1-C5 alkyl, halogen, C1-C10 alkoxy, or with a phenyl group substituted with halogen, C1-C5 alkyl or C1-C5 alkoxy, or with a functional group;
• X is an anionic ligand;
• L is a nucleophilic carbene;
• Ar is an aryl substituent, bonded to M by an η6 bond;
• and
• A− is an inorganic anion or an organic anion.

A catalytic complex of the formula:

• wherein M is Os or Ru;
• in which carbon atom C is bonded to up to two groups R and R1;
• R and R1 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C2-C20 alkoxycarbonyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy C2-C20 alkynyloxy, aryloxy, C1-C20 alkylthio, C1-C20 alkylsulfonyl, and C1-C20 alkylsulfinyl each R and R1 optionally being substituted with C1-C5 alkyl, halogen, C1-C10 alkoxy, or with a phenyl group substituted with halogen, C1-C5 alkyl or C1-C5 alkoxy, or with a functional group;
• X and X1 are independently selected from the group consisting of anionic ligands;
• L is selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, ether, amine, amide, sulfoxide, carbonyl, nitrosyl, pyridine and thioether;
• and
• L1 is of the formula
• wherein Y and Y′ are each independently an aryl group substituted with halogen, C1-C5 alkyl, or C1-C5 alkoxy, or with a phenyl group substituted with halogen, C1-C5 alkyl or C1-C5 alkoxy;
• and
• Z and Z1 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C2-C20 alkoxycarbonyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, and aryloxy, each Z and Z1 optionally being substituted with C1-C5 alkyl, halogen, C1-C5 alkoxy, or with a phenyl group substituted with halogen, C1-C5 alkyl or C1-C5 alkoxy.

A catalytic complex of the formula:

• wherein
• L is selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, ether, amine, amide, sulfoxide, carbonyl, nitrosyl, pyridine and thioether;
• and
• L1 is a nucleophilic carbene, wherein L1 is of the formula
• wherein Y and Y1 are each independently an aryl group substituted with halogen, C1-C5 alkyl, or C1-C5 alkoxy, or with a phenyl group substituted with halogen, C1-C5 alkyl or C1-C5 alkoxy;
• and
• Z and Z1 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20-alkynyl, C21-C20 alkoxycarbonyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, and aryloxy, each Z and Z1 optionally being substituted with C1-C5 alkyl, halogen, C1-C5 alkoxy, or with a phenyl group substituted with halogen, C1-C5 alkyl or C1-C5 alkoxy.

A catalytic complex of the formula:

• wherein
• L is selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, ether, amine, amide, sulfoxide, carbonyl, nitrosyl, pyridine and thioether;
• and
• L1 is a nucleophilic carbene, wherein L1 is of the formula
• wherein Y and Y1 are each independently an aryl group substituted with halogen, C1-C5 alkyl, or C1-C5 alkoxy, or with a phenyl group substituted with halogen, C1-C5 alkyl or C1-C5 alkoxy;
• and
• Z and Z1 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C2-C20 alkoxycarbonyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, and aryloxy, each Z and Z1 optionally being substituted with C1-C5 alkyl, halogen, C1-C5 alkoxy, or with a phenyl group substituted with halogen, C1-C5 alkyl or C1-C5 alkoxy.

A catalytic complex of the formula:

• wherein M is Os or Ru;
• R and Z1 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C2-C20 alkoxycarbonyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C1-C20 alkylthio, C1-C20 alkylsulfonyl, and C1-C20 alkylsulfinyl, each R and R1 optionally being substituted with C1-C5 alkyl, halogen, C1-C10 alkoxy, or with a phenyl group substituted with halogen, C1-C5 alkyl or C1-C5 alkoxy, or with a functional group;
• X and X1 are independently selected from the group consisting of anionic ligands;
• L is selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, ether, amine, amide, sulfoxide, carbonyl, nitrosyl, pyridine and thioether;
• L1 is a nucleophilic carbene;
• and
• wherein the catalytic complex has one or more further characterization selected from the group consisting of
• (1) at least 2 of X, X1, L or L1 are bonded together to form a multidentate ligand;
• (2) the complex is linked to a solid support by means of a link between the solid support and the nucleophilic carbene or by means of a link between the solid support and at least one of the anionic ligands;
• (3) L1 has the formula
• where Y and Y1 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C2-C20 alkoxycarbonyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, and aryloxy, each Y and Y1 optionally being substituted with C1-C5 alkyl, halogen, C1-C6 alkoxy, or with a phenyl group substituted with halogen, C1-C5 alkyl or C1-C5 alkoxy;
• and
• Z and Z1 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C2-C20 alkoxycarbonyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, and aryloxy, each Z and Z1 optionally being substituted with C1-C5 alkyl, halogen, C1-C6 alkoxy, or with a phenyl group substituted with halogen, C1-C5 alkyl or C1-C5 alkoxy;
• and
• (4) any combination of the foregoing characteristics.

A catalytic complex of the formula:

• wherein M is Os or Ru;
• R is hydrogen;
• R1 is tert-butyl;
• X and X1 are chloride;
• L is selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, ether, amine, amide, sulfoxide, carbonyl nitrosyl, pyridine and thioether;
• and
• L1 is a nucleophilic carbene of the formula
• where Y and Y1 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C2-C20 alkoxycarbonyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, and aryloxy, each Y and Y1 optionally being substituted with C1-C5 alkyl, halogen, C1-C6 alkoxy, or with a phenyl group substituted with halogen, C1-C5 alkyl or C1-C5 alkoxy;
• and
• Z and Z1 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C2-C20 alkoxycarbonyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, and aryloxy, each Z and Z1 optionally being substituted with C1-C5 alkyl, halogen, C1-C6 alkoxy, or with a phenyl group substituted with halogen, C1-C5 alkyl or C1-C5 alkoxy.