Transition metal-phosphoranimide catalysts
AssigneeThe Governors of the University of Alberta
InventorsJeffrey Camacho BUNQUIN, Jeffrey Mark STRYKER
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Abstract
Phosphoranimide-metal catalysts are disclosed. The catalysts comprise first row transition metals such as nickel, cobalt or iron. The hydrocarbon-soluble catalysts have a metal to anionic phosphoranimide ratio of 1:1, have no inactive bulk phase and no dative ancillary ligands, and are active for a range of commercially important reductive transformations. A method of synthesis of these catalysts by reduction of a precursor of these catalysts is also disclosed.
Claims23
A transition metal catalyst comprising monomeric units of the general Formula I:
- [MNPR3] Formula I
- where M is a first row transition metal having a +1 oxidation state;
- R3PN− is a monoanioinic phosphoranimide ligand of structure:
- where:
- R1, R2, R3 can be the same group or different groups;
- R1, R2, R3=alkyl (C1-18, primary, secondary and tertiary alkyl), cycloalkyl (C3-C8), aryl/heteroaryl, substituted aryl/heteroaryl or an inert functional group containing at least one heteroatom selected from the group consisting of a Group 15 and/or Group 16 element;
- R1, R2, R3 may also be linked to give cyclic systems, using linkages such as aliphatic cyclic systems;
- wherein the M to R3PN− ratio in the catalyst is 1:1.
A method of synthesis of a transition metal catalyst comprising:
- reducing a complex of Formula IV [MNPR3X(m-1)]n with a reducing agent to produce a catalyst of Formula I [MNPR3], wherein Formula IV is
- [MNPR3X(m-1)]n
- where:
- m=2 to 3;
- n=1 to 4;
- M is Fe, Co or Ni;
- X− can be any halide or pseudohalide;
- R3PN− is a monoanioinic phosphoranimide ligand of structure:
- where
- R1, R2, R3 are the same group or different groups;
- R1, R2, R3=alkyl (C1-18, primary, secondary and tertiary alkyl), cycloalkyl (C3-C8), aryl/heteroaryl, substituted aryl/heteroaryl or an inert functional group optionally containing at least one heteroatom, and wherein the substituents may also be linked to give cyclic systems, both aliphatic and aromatic;
- the M:NPR3 ratio is 1:1;
- and wherein in Formula I, M and NPR3 are as defined for the compound of Formula II and wherein the M:NPR3 ratio is 1:1.
A method of synthesis of complex of Formula IV from an anionic metathesis reaction between a metal salt selected from the group consisting of MXm and LaMXm and an alkali or alkaline metal salt of a phosphoranimide ligand, wherein Formula IV is defined as follows:
- [MNPR3X(m-1)]n
- where:
- m=2 to 3;
- n=1 to 4;
- M is Fe, Co or Ni.
- X− can be any halide or pseudohalide;
- R3PN− is a monoanioinic phosphoranimide ligand of structure:
- Where:
- R1, R2, R3 can be the same group or different groups;
- R1, R2, R3=alkyl (C1-18, primary, secondary and tertiary alkyl), cycloalkyl (C3-C8), aryl/heteroaryl, substituted aryl/heteroaryl or an inert functional group optionally containing at least one heteroatom, and wherein the substituents may also be linked to give cyclic systems, both aliphatic and aromatic;
- the ratio of NPR3 to M is 1:1;
- and
- wherein in MXm and LaMXm:
- m=2 to 3;
- a=1 to 4;
- M can be any first row transition metals;
- X− can be any halide or pseudohalide;
- L can be a two-electron dative donor molecule selected from the group of dialkyl ethers consisting of tetrahydrofuran, 1,2-dimethoxyethane, dioxane;
- or selected from the group consisting of trialkylphosphine or a triarylphosphine selected from the group consisting of triphenylphosphine and tri-(p-tolyl)phosphine.
Dependencies are inferred from the claim text.