Hydrosilylation process in the presence of ruthenium catalyzers

A process for hydrosilylation comprising reacting at least one Si—H functionality with at least one hydrosilylatable unsaturated carbon-carbon bond in the presence of a ruthenium catalyst having at least two independent carbon π-bonded ligands, at least one of these ligands being selected from the group consisting of η6-bonded arene ligands, η6-bonded triene ligands, η4-bonded 1,5-cyclooctadiene ligands and η4-bonded 1,3,5-cyclooctatriene ligands wherein the ruthenium catalyst is at least one catalyst selected from the group consisting of compounds of the formula (3)

• where
• R1 to R4 are each independently hydrogen, alkyl, aryl, halogen, silyl, siloxy, CN, CO2R″ where R″ is hydrogen or alkyl, or CHO or C(O)R′″ where R′″ is alkyl or aryl;
• and
• L is PR3′″ or P(OR′″)3, where R′″ is alkyl or aryl, NR2H where R is hydrogen, alkyl or alkylaryl, morpholine, or pyridine;
• compounds of the formula (5)
• where
• R1 to R4 are each independently hydrogen, alkyl, aryl, halogen, silyl, siloxy, CN, CO2R″ where R″ is hydrogen or alkyl, or CHO or C(O)R′″ where R′″ is alkyl or aryl;
• and
• L1 and L2 are each independently CO, CNR′″ where R′″ is alkyl or aryl, PR3′″ or P(OR′″)3 where R′″ is alkyl or aryl, ligands containing N donors, ligands containing S donors, and ligands containing O donors, with the proviso that L1 and L2 may optionally be joined to one another and optionally form a ring;
• compounds of the formula (6)
• where R1 to R5 are each independently hydrogen, alkyl, or aryl, and the dotted line in the formula (6) represents one or more conjugated or nonconjugated double bonds;
• n is 0, 2 or 3;
• and
• X is any monovalent anionic ligand;
• or compounds of the formula (7)
• where
• R1 to R3 are each independently hydrogen or alkyl.

A hydrosilylatable composition useful in a process of hydrosilation comprising

• (A) at least one compound with at least one silicon-hydrogen bond, and
• (B) at least one compound with at least one aliphatically unsaturated carbon-carbon bond,
• (D) a ruthenium compound having a ligand sphere comprising at least two independent carbon π-bonded ligands, at least one of these ligands being selected from the group consisting of η6-bonded arene ligands, η6-bonded triene ligands, η4-bonded 1,5-cyclooctadiene ligands and η4-bonded 1,3,5-cyclooctatriene ligands, wherein at least one ruthenium compound is selected from the group consisting of compounds of the formula (3)
• where
• R1 to R4 are each independently hydrogen, alkyl, aryl, halogen, silyl, siloxy, CN, CO2R″ where R″ is hydrogen or alkyl, or CHO or C(O)R′″ where R″′ is alkyl or aryl;
• and
• L is PR3′″ or P(OR′″)3, where R′″ is alkyl or aryl, NR2H where R is hydrogen, alkyl or alkylaryl, morpholine, or pyridine;
• compounds of the formula (5)
• where
• R1 to R4 are each independently hydrogen, alkyl, aryl, halogen, silyl, siloxy, CN, CO2R″ where R″ is hydrogen or alkyl, or CHO or C(O)R′″ where R′″ is alkyl or aryl;
• and
• L1 and L2 are each independently CO, CNR′″ where R′″ is alkyl or aryl, PR3′″ or P(OR′″)3 where R′″ is alkyl or aryl, ligands containing N donors, ligands containing S donors, and ligands containing O donors, with the proviso that L1 and L2 may optionally be joined to one another and optionally form a ring;
• compounds of the formula (6)
• where R1 to R5 are each independently hydrogen, alkyl, or aryl, and the dotted line in the formula (6) represents one or more conjugated or nonconjugated double bonds;
• n is 0, 2 or 3;
• and
• X is any monovalent anionic ligand;
• and
• compounds of the formula (7)
• where
• R1 to R3 are each independently hydrogen or alkyl.

A process for hydrosilylation comprising reacting at least one Si—H functionality with at least one hydrosilylatable unsaturated carbon-carbon bond in the presence of a ruthenium catalyst having at least two independent carbon π-bonded ligands, at least one of these ligands being selected from the group consisting of η6-bonded arene ligands, η6-bonded triene ligands, η4-bonded 1,5-cyclooctadiene ligands and η4-bonded 1,3,5-cyclooctatriene ligands wherein the ruthenium catalyst is a compound selected from the group consisting of a compound of the formula (2)

• where
• R1 to R8 are each independently hydrogen, alkyl, aryl, halogen, silyl, siloxy, CN, CO2R″ where R″ is hydrogen or alkyl, CHO, or C(O)R′″ where R′″ is alkyl, aryl or NR2 where R is hydrogen or alkyl, and
• x=1 and y=2;
• x=2 and y=2;
• or
• x=2 and y=4.

A process for hydrosilylation comprising reacting at least one Si—H functionality with at least one hydrosilylatable unsaturated carbon-carbon bond in the presence of a ruthenium catalyst having at least two independent carbon π-bonded ligands, at least one of these ligands being selected from the group consisting of η6-bonded arene ligands, η6-bonded triene ligands, η4-bonded 1,5-cyclooctadiene ligands and η6-bonded 1,3,5-cyclooctatriene ligands wherein the ruthenium catalyst is selected from the group consisting of compounds of the formula (4)

• where
• R1 to R8 are each independently hydrogen, alkyl, aryl, halogen, silyl, siloxy, CN, CO2R″ where R″ is hydrogen or alkyl, or CHO or C(O)R′″ where R′″ is alkyl or aryl, with the proviso that radicals from R1 to R4 and R5 to R8, with or without additional spacing groups, may optionally be joined to one another forming, a polydentate acyclic or cyclic ligand;
• and
• L is CO;
• CNR′″ where R′″ is alkyl or aryl, ligands containing S donors, and ligands containing O donors.