Transition metal catalysts for c-o hydrogenolysis and hydrodeoxygenation
AssigneeThe Governors of the University of Alberta
InventorsJeffrey Camacho Bunquin, Jeffrey Mark Stryker
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Abstract
Phosphoranimide-metal catalysts and their role in C—O bond hydrogenolysis and hydrodeoxygenation (HDO) are disclosed. The catalysts comprise of first row transition metals such as nickel, cobalt and iron. The catalysts have a metal to anionic phosphoranimide ratio of 1:1 and catalyze C—O bond hydrogenolyses of a range of oxygen-containing organic compounds under lower temperature and pressure conditions than those commonly used in industrial hydrodeoxygenation.
Claims26
A method of catalyzing a C—O bond hydrogenolysis reaction comprising:
- reacting an organic substrate having at least one carbon-oxygen bond with a reducing agent and catalyst of general formula:
- [M(NPR3)]n
- where:
- M is a first row transition metal having a +1 oxidation state;
- n is a whole number of at least 2;
- the ratio of M to R3PN− ratio is 1:1;
- R3PN− is a monoanioinic phosphoranimide ligand of structure:
- where:
- R1, R2, R3 can be the same group or different groups;
- R1, R2, R3 are independently alkyl (C1-18, primary, secondary or tertiary alkyl), cycloalkyl (C3-C8), aryl/heteroaryl, substituted aryl/heteroaryl or an inert functional group containing at least one heteroatom;
- and
- R1, R2, R3 may be linked to give cyclic systems.
The method of claim 22, wherein X− is F−, Cl−, Br−, I−, or OSO2R−, where R=Me, Ph, p-Tol, CF3.
A method of catalyzing the C—O bond hydrogenolysis of an organic compound having at least one carbon-oxygen bond comprising:
- reacting the organic substrate with a compound selected from the group consisting of [Fe(NPtBu3)]4, [Co(NPtBu3)]4 and [Ni(NPtBu3)]4.
A method of catalyzing the C—O bond hydrogenolysis of an organic substrate comprising:
- reacting the organic substrate with a catalyst of Formula [M(NPR3)]n
- wherein n is a whole number of at least 2;
- the ratio of M to NPR3 is 1:1;
- M is a first row transition metal selected from the group consisting of Fe, Co and Ni;
- NPR3 is:
- where:
- R1, R2, R3 are independently alkyl (C1-18, primary, secondary or tertiary alkyl), cycloalkyl (C3-C8), aryl/heteroaryl, substituted aryl/heteroaryl and an inert functional group containing at least one heteroatom selected from a Group 14, Group 15 and Group 16 element, preferably Si, N, and O.
- wherein R1, R2, R3 may also be linked by aliphatic groups to give cyclic systems;
- wherein the reaction is carried out at a temperature range of about 50 to 300° C. in the presence of a reducing agent selected from the group consisting of hydrogen and an organic silyl hydride;
- and
- wherein the reaction is carried out in toluene or tetrahydrofuran.
A process for C—O bond hydrogenolysis of an organic substrate having at least carbon-oxygen bond comprising:
- (i) combining the said organic substrate with a transition metal complex of Formula II and a reductant selected from hydrogen and an organic silyl hydride to obtain a reaction medium;
- (ii) allowing the catalyst to catalyze the C—O bond hydrogenolysis of the substrate in an organic substrate selected from toluene and tetrahydrofuran;
- (iii) obtaining the hydrogenolysis products derived from the organic substrate;
- wherein the organic substrate is an aromatic or aliphatic compound containing at least one carbon-oxygen bond;
- and
- wherein the complex of Formula II is:
- [M(NPR3)]n Formula II
- where
- n is a whole number of at least 2;
- the ratio of M to NPR3 is 1:1;
- M is a first row transition metalselected from the group consisting of Fe, Co and Ni;
- NPR3 is:
- where:
- R1, R2, R3 are independently alkyl (C1-18, primary, secondary or 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 14, Group 15 and Group 16;
- and wherein R1, R2, R3 may also be linked by aliphatic groups to give cyclic systems.
Dependencies are inferred from the claim text.