Immobilized metal alkylidene catalysts and use thereof in olefin metathesis

A compound of general Formula I or Formula II

• wherein:
• A1 is NR2 or PR2;
• A2 is CR2R2′, NR2, PR2, O or S;
• C is a carbene carbon atom;
• ring B includes A1—C—A2 and is a unsubstituted or mono- or multisubstituted 5 to 7-membered ring, which may contain besides A1 and A2 further heteroatoms selected from nitrogen, phosphorus, oxygen or sulfur, and the substituents of which have the meaning of R2;
• R2 and R2′ are independently from one another H, a linear, a partially cyclic or branched C1 to C18-alkyl residue, a linear, a partially cyclic or branched C1 to C18-alkenyl residue, a C3 to C12-cycloalkyl residue, a linear, partially cyclic or branched C6 to C100-polyoxaalkyl residue, a C5 to C14-aryl or heteroaryl residue, a C3 to C14-aryloxy residue, a linear, partially cyclic or branched C1 to C18-perfluoroalkyl residue, a linear, partially cyclic or branched C1 to C18-perchloroalkyl residue, a linear, partially cyclic or branched partially fluorinated C1 to C18-alkyl residue, a partially chlorinated linear, partially cyclic or branched C1 to C18-alkyl residue, a perfluorinated or partially fluorinated C6 to C14-aryl residue, a perchlorinated or partially chlorinated C6 to C14-aryl residue;
• and, when A1 and A2 are NR2 or PR2, respectively, R2 may be the same or may be different, or
• R2 and R2′ taken together form a linear or branched C1 to C18-alkylene residue;
• M is Cr, Mo or W;
• X1 is a residue of a solid oxide, wherein the solid oxide is linked to M via oxygen;
• X2 is selected from the group comprising or consisting of halogenide, C1 to C18-carboxylates, C1 to C18-alkoxides, fluorinated C1 to C18-alkoxides, C1 to C18-mono- or polyhalogenated carboxylates, unsubstituted, mono or multisubstituted C6 to C18-monophenolate, -biphenolate or -terphenolate, wherein the substituents at the monophenolate, bisphenolate or terphenolate have the meaning of halogen or R2, C1 to C18-thiolate, unsubstituted, mono or multisubstituted C6 to C18-monothiophenolate, -thiobiphenolate or -thioterphenolate, wherein the substituents at the thiomonophenolate, thiobisphenolate or thioterphenolate have the meaning of halogen or R2, trifluoromethane sulfonate, pyrrol-1-yl, optionally substituted with one or more of R2, —NH—(CO)—R2, —N(R2)2, wherein R2 is selected independently from one another, or non-coordinating anions;
• Y is oxygen, sulfur, N-adamantyl, N-tert-butyl, N—(C6-14)aryl, wherein aryl may be substituted with one or more of halogen, linear or branched C1 to C18-alkyl, linear or branched C1 to C18-alkyloxy or substituted or unsubstituted phenyl, the substituents of which have the meaning of R2;
• R1 and R1′ are independently from one another H, linear or branched C1 to C18-alkyl or unsubstituted or substituted C6 to C14-aryl, wherein the substituents have the meaning of R2;
• or R1 and R1′ are independently from one another ortho-alkoxyphenyl, wherein alkoxy is C1 to C6-alkoxy;
• or wherein R1 and R1′ are independently from one another H and ortho-alkoxyphenyl, wherein alkoxy is C1 to C6-alkoxy.