Phosphinimine methanide transition metal catalysts

A complex of formula I:

• 13
• wherein M is a metal atom;
• R1, R2, R3 and R4 are independently selected from the group consisting of a saturated or unsaturated straight chained, branched or cyclic hydrocarbyl radical which is unsubstituted or substituted by one or more substituents selected from the group consisting of a halogen atom and a C1-6 alkyl radical;
• R7 and R8 are independently selected from the group consisting of a halogen atom, an amide of the formula —NR1R2, imide of the formula ═NR1, alkoxide or aryl oxide group of the formula —OR1, a siloxy group of the formula —OSi(R1)3 wherein R1 and R2 are defined above, and a saturated or unsaturated straight chained, branched or cyclic hydrocarbyl radical which is unsubstituted or substituted by a halogen atom or a C1-6 alkyl radical and a Lewis base (neutral coordinating ligands);
• a and b are integers and a+b is an integer greater than 2 up to the sum of the valence and coordination number of M;
• and each R5 is independently selected from the group consisting of radicals selected from the group consisting of saturated and unsaturated straight chained, branched and cyclic hydrocarbyl radicals, radicals of the formula Si(R6)3 wherein each R6 is independently selected from the group consisting of saturated or unsaturated straight chained, branched or cyclic hydrocarbyl radicals, preferably C1-10 saturated or unsaturated straight chained, branched or cyclic hydrocarbyl radicals and radicals of the formula III:
• 14
• wherein R9, R10, R11 and R12 are independently selected from the group consisting of a hydrogen atom, a fluorine atom, a NO2 radical, a C1-6 alkyl radical and a C8-12 aryl radical;
• and E is an endocyclic nitrogen atom or a C—CN group;
• and R14 is selected from the group consisting of a hydrogen atom, a sulfur atom, an oxygen atom, an amido radical which is unsubstituted or may be substituted by C1-20 alkyl radical or a radical of the formula —Si(R6)3 wherein R6 is as defined above, a C1-20 hydrocarbyl radical, a C6-12 aromatic radical and a radical of the formula III as defined above, each of which may contain one or more functional groups including a heteroatom acting as a Lewis base;
• and optionally R14 taken together with M may form a ring.

A process for preparing a complex of formula I:

• 17
• wherein M is a metal atom;
• R1, R2, R3 and R4 are independently selected from the group consisting of a saturated or unsaturated straight chained, branched or cyclic hydrocarbyl radical which is unsubstituted or substituted by one or more substituents selected from the group consisting of a halogen atom and a C1-6 alkyl radical;
• R7 and R8 are independently selected from the group consisting of a halogen atom, an amide of the formula —NR1R2, an imide of the formula ═NR1, an alkoxide or aryl oxide group of the formula —OR1, a siloxy group of the formula —OSi(R1)3 wherein R1 and R2 are defined above, and a saturated or unsaturated straight chained, branched or cyclic hydrocarbyl radical which is unsubstituted or substituted by a halogen atom or a C1-6 alkyl radical and a Lewis base (neutral coordinating ligands);
• a and b are integers and a+b is an integer greater than 2 up to the sum of the valence and coordination number of M;
• and each R5 is independently selected from the group consisting of radicals selected from the group consisting of saturated and unsaturated straight chained, branched and cyclic hydrocarbyl radicals, radicals of the formula Si(R6)3 wherein each R6 is independently selected from the group consisting of saturated or unsaturated straight chained, branched or cyclic hydrocarbyl radicals and radicals of the formula III:
• 18
• wherein R9, R10, R11 and R12 are independently selected from the group consisting of a hydrogen atom, a fluorine atom, a NO2 radical, a C1-6 alkyl radical and a C8-12 aryl radical;
• E is an endocyclic nitrogen atom or a C—CN group;
• and R14 is selected from the group consisting of a hydrogen atom, a sulfur atom, an oxygen atom, an amido radical which is unsubstituted or may be substituted by C1-20 alkyl radical or a radical of the formula —Si(R6)3 wherein R6 is as defined above, a C1-20 hydrocarbyl radical, a C6-12 aromatic radical and a radical of the formula III as defined above, each of which may contain one or more functional groups including a heteroatom acting as a Lewis base;
• and optionally R14 taken together with M may form a ring comprising reacting a complex of formula II:
• 19
• wherein R1, R2, R3, R4, R5, R7, R8, a, b and M are as defined above with:
• (i) molecules of the type AB where in A is selected from the group consisting of a hydrogen atom, a C1-20 alkyl group, a C6-12 aryl group, an amido radical which is unsubstituted or may be substituted by C1-20 alkyl radical or a radical of the formula —Si(R6)3 wherein R6 is as defined above, an C1-20 alkoxy group, a C1-20 alkylthio group, a C6-12 aryloxy group, a C6-12 arylthio group, and a radical of the formula III as defined above;
• and B is selected from the group consisting of a hydrogen atom provided that A is not a hydrocarbyl radical or a hydrogen atom, and halogen atom;
• (ii) compounds of the formula F=C=G wherein F and G are independently selected from the group consisting of an O or S atom, and radicals of the formula ═N—R15, wherein R15 is a C1-20 hydrocarbyl radical, a C6-12 aromatic radical, and a radical of the formula —Si(R6)3 wherein R6 is as defined above;
• ═P—(R16)d wherein d is 1 or 3;
• and R16 is selected from the group consisting of a hydrogen atom, a halogen atom, C1-20 hydrocarbyl radical, a C1-20 alkoxide radical, a C6-12 aromatic radical, a C6-12 aryloxide radical, and radicals of the formula —Si(R6)3 or —O—Si(R6)3 wherein R6 is as defined above.