Selective isomerization and linear dimerization of olefins using cobalt catalysts

A process for the production of alpha-olefins, comprising:

• contacting a Co[I] or Co[II] or Co[III] complex of a tridentate ligand of Formula II with an alpha-olefin,
• wherein
• R1, R2 and R3 are each independently hydrogen, fluorine, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
• R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
• R9, R10, R11, R14, R15 and R16 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
• R8 and R17 are each hydrogen, fluorine, an inert functional group, a primary carbon group, a secondary carbon group or a tertiary carbon group;
• and provided that:
• when R8 is a primary carbon group none, one or two of R12, R13 and R17 are primary carbon groups, and the remainder of R12, R13 and R17 are hydrogen or fluorine;
• when R8 is a secondary carbon group, none or one or two of R12, R13 and R17 is a primary carbon group or a secondary carbon group or an inert functional group and the remainder of R12, R13, and R17 are hydrogen or fluorine;
• when R8 is a tertiary carbon group all of R12, R13 and R17 are hydrogen or fluorine;
• any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 vicinal to one another, taken together may form a ring;
• a Co[I] or Co[II] or Co[III] atom also has bonded to it an empty coordination site or a ligand that may be displaced by said alpha-olefin, and a ligand that may add to said alpha-olefin.

A process for the production of alpha-olefins, comprising:

• contacting an alpha-olefin and a compound of Formula III, Formula IV, or Formula V:
• wherein:
• R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
• R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group, or substituted hydrocarbyl,
• R9, R10, R11, R14, R15 and R16 are each independently hydrogen, hydrocarbyl, an inert functional group, or substituted hydrocarbyl;
• R8 and R17 are each hydrogen, fluorine, an inert functional group, a primary carbon group, a secondary carbon group or a tertiary carbon group;
• T1 is hydride or alkyl or any other anionic ligand into which an alpha-olefin can insert;
• Y is a vacant coordination site, or a neutral ligand capable of being displaced by an alpha-olefin;
• and
• P is an alkyl group;
• and provided that:
• when R8 is a primary carbon group none, one or two of R12, R13 and R17 are primary carbon groups, and the remainder of R12, R13 and R17 are hydrogen or fluorine;
• when R8 is a secondary carbon group, none or one of R12, R13 and R17 is a primary carbon group or a secondary carbon group and the remainder of R12, R13, and R17 are hydrogen or fluorine;
• when R8 is a tertiary carbon group all of R12, R13 and R17 are hydrogen or fluorine;
• and any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 vicinal to one another, taken together may form a ring.

A process for the dimerization of alpha-olefins comprising:

• contacting a compound of Formula I:
• with an alpha-olefin and:
• (a) a first compound W, which is a neutral Lewis acid capable of abstracting X−, an alkyl group, or a hydride group from Co to form WX−, (WR20)− or WH− and which is also capable of transferring an alkyl group or a hydride to Co, provided that WX− is a weakly coordinating anion;
• or
• (b) a combination of second compound which is capable of transferring an alkyl or hydride group to Co and a third compound which is a neutral Lewis acid which is capable of abstracting X−, a hydride or an alkyl group from Co to form a weakly coordinating anion;
• wherein:
• each X is an anion;
• n is 1, 2 or 3 so that the total number of negative charges on said anion or anions is equal to the oxidation state of a Co atom present in Formula I;
• R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
• R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
• R9, R10, R11, R14, R15 and R16 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
• R8 and R17 are each hydrogen, fluorine, an inert functional group, a primary carbon group, a secondary carbon group or a tertiary carbon group;
• and
• R20 is alkyl;
• and provided that:
• when R8 is a primary carbon group none, one or two of R12, R13 and R17 are primary carbon groups, secondary carbon groups, or inert functional groups, and the remainder of R12, R13, and R17 are hydrogen or fluorine;
• when R8 is a secondary carbon group, none or one or two of R12, R13 and R17 is a primary carbon group or a secondary carbon group or an inert functional group and the remainder of R12, R13, and R17 are hydrogen or fluorine;
• when R8 is a tertiary carbon group all of R12, R13, and R17 are hydrogen or fluorine;
• and any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 vicinal to one another, taken together may form a ring.

A process for the isomerization of alpha-olefins to internal olefins comprising:

• contacting a compound of Formula I:
• with an alpha-olefin and:
• (a) a first compound W, which is a neutral Lewis acid capable of abstracting X−, an alkyl group, or a hydride group from Co to form WX−, (WR20)− or WH− and which is also capable of transferring an alkyl group or a hydride to Co, provided that WX− is a weakly coordinating anion;
• or
• (b) a combination of second compound which is capable of transferring an alkyl or hydride group to Co and a third compound which is a neutral Lewis acid which is capable of abstracting X−, a hydride or an alkyl group from Co to form a weakly coordinating anion;
• wherein:
• each X is an anion;
• n is 1, 2 or 3 so that the total number of negative charges on said anion or anions is equal to the oxidation state of a Co atom present in Formula I;
• R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
• R4 and R5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
• R9, R10, R11, R14, R15 and R16 are each independently hydrogen, hydrocacbyl, an inert functional group or substituted hydrocarbyl;
• R8 and R17 are each hydrogen, fluorine, an inert functional group, a primary carbon group, a secondary carbon group or a tertiary carbon group;
• and
• R20 is alkyl;
• and provided that:
• when R8 is a primary carbon group none, one or two of R12, R13 and R17 are primary carbon groups, secondary carbon groups, or inert functional groups, and the remainder of R12, R13, and R17 are hydrogen or fluorine;
• when R8 is a secondary carbon group, none or one or two of R12, R13 and R17 is a primary carbon group or a secondary carbon group or an inert functional group and the remainder of R12, R13, and R17are hydrogen or fluorine;
• when R8 is a tertiary carbon group all of R12, R13, and R17 are hydrogen or fluorine;
• and
• any two of R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 vicinal to one another, taken together may form a ring.

A process for oligomerizing alpha-olefins comprising:

• contacting a compound of Formula I:
• with an alpha-olefin wherein if said olefin is propylene, then the oligomerization process proceeds by a step growth mechanism, and:
• (a) a first compound W, which is a neutral Lewis acid capable of abstracting X−, an alkyl group, or a hydride group from Co to form WX−, (WR20)− or WH− and which is also capable of transferring an alkyl group or a hydride to Co, provided that WX− is a weakly coordinating anion;
• or
• (b) a combination of second compound which is capable of transferring an alkyl or hydride group to Co and a third compound which is neutral Lewis acid which is capable of abstracting X−, a hydride or an alkyl group from Co to form a weakly coordinating anion;
• wherein
• each X is an anion;
• n is 1, 2 or 3 so that the total number of negative charges on said anion or anions is equal to the oxidation state of a Co atom present in Formula I;
• R1, R2 and R3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
• R4 and R5 are each independently hydrogen, hydrocarbyl, and inert functional group or substituted hydrocarbyl;
• R9, R10, R11, R14, R15 and R16 are each independently hhydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
• R8 and R17 are each hydrogen, fluorine, an inert functional group, a primary carbon group, a secondary carbon group or a tertiary carbon group;
• and
• R20 is alkyl;
• and provided that:
• when R8 is a primary carbon group none, one or two of R12, R13, and R17 are primary carbon groups, secondary carbon groups, or inert functional groups, and the remainder of R12, R13, and R17 are hydrogen or fluorine;
• when R8 is a secondary carbon group, none or one or two of R12, R13 and R17 is a primary carbon group or a secondary carbon group or an inert functional group and the remainder of R12, R13, and R17 are hydrogen or fluorine;
• when R8 is a tertiary carbon group all of R12, R13, and R17 are hydrogen or fluorine;
• and any two of R8, R9, R10, R11, R12, R13, R14, R15 and R16 vicinal to one another, taken together may form a ring.