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US 9,000,198 B2Granted
Mixed-valent transition metal-phosphoranimide catalysts
AssigneeThe Governors of the University of Alberta
InventorsHouston J. S. Brown, Jeffrey Mark Stryker, Dominque M. Hebert
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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, and have no inactive bulk phase and no dative ancillary ligands. The electronic state of the clusters can be adjusted to optimize catalytic activity for a range of commercially important reductive transformations, including hydrodesulfurization. A method of synthesis of these catalysts by anionic metathesis of a halide substituted precursor followed by oxidation is also disclosed.
Claims25
A compound of Formula I, wherein Formula I has the structure:
- {[A-M(NPR3)]n}m+(Yd−)e Formula I
- where:
- A is a monoanionic σ-bonded ligand that undergoes hydrogenolysis in the presence of hydrogen or hydrosilane;
- M is a late first row transition metal;
- n equals 2 to 4;
- m equals 0 to 4 up to a maximum value of n;
- Y is a weakly-coordinating or non-coordinating counter-ion, of formal negative charge ‘d’, and with stoichiometry ‘e’ such that d·e=m, and the charge of the counter-ion(s) offsets that of the cluster;
- R3PN is an anionic 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, and silicon;
- R1, R2, R3 may also be linked to give cyclic systems, using linkages such as aliphatic cyclic systems;
- and
- wherein the M to R3PN− ratio is 1:1.
11 more elements
A method for synthesizing a compound of Formula II:
- [A-M(NPR3)]n
- where:
- A is a monoanionic σ-bonded ligand that undergoes hydrogenolysis in the presence of hydrogen or hydrosilane;
- M is Co, Ni or Fe;
- n equals 2 to 4;
- R3PN is an anionic 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 Group 16 element, and silicon;
- R1, R2, R3 may also be linked to give cyclic systems;
- and wherein the M to R3PN− ratio in the catalyst is 1:1,
- the method comprising:
- reacting a precursor of Formula III:
- [(MNPR3)nXm], where M, NPR3, and X are as defined for the compound of Formula II and m=2 to 4, with a nucleophilic reagent AM′ comprising the anion of A where M′ is alkali or alkaline earth metal, or a Group 13 reagent.
11 more elements
A method of synthesis of the compound of Formula I having formula:
- {[A-M(NPR3)]n}m+(Yd−)e Formula I
- where:
- A is a monoanionic σ-bonded ligand that undergoes hydrogenolysis in the presence of hydrogen or hydrosilane;
- M is a late first row transition metal;
- n equals 2 to 4;
- m equals 0 to 4 up to a maximum value of n;
- Y is a weakly-coordinating or non-coordinating counter-ion, of formal negative charge ‘d’, and with stoichiometry ‘e’ such that d·e=m, and the charge of the counter-ion(s) offsets that of the cluster;
- R3PN is an anionic 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 Group 16 element, and silicon;
- R1, R2, R3 may also be linked to give cyclic systems, using linkages such as aliphatic cyclic systems;
- and wherein the M to R3PN− ratio is 1:1,
- the method comprising:
- reacting a compound of Formula II:
- [A-M(NPR3)]n
- wherein A, M, n and NPR3 are defined as in the compound of Formula I with an outer sphere oxidant.
14 more elements
A method of synthesis of a complex of Formula III:
- [(MNPR3)nXm] Formula III
- where:
- m=2 to 4;
- n=2 to 4;
- M is Fe, Co or Ni;
- X can be any halide or pseudohalide;
- R3PN is an anionic 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 method comprising:
- conducting 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:
- m on MXm and LaMXm=2 to 3;
- a=1 to 4;
- M is Co, Ni or Fe;
- X is a halide or pseudohalide;
- L is a two-electron dative donor molecule selected from tetrahydrofuran, 1,2-dimethoxyethane, dioxane a dissociable trialkylphosphine and a triarylphosphine ligand;
- and wherein phosphoranimide ligand, NPR3, is defined as in the compound of Formula III.
14 more elements
Dependencies are inferred from the claim text.