Transition metal catalysts for hydrogenation and hydrosilylation
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 hydrogenation and hydrosilylation are disclosed. The catalysts comprise first row transition metals such as nickel, cobalt or iron. The catalysts have a metal to anionic phosphoranimide ratio of 1:1. This disclosure presents a process for catalytic hydrogenation and hydrosilylation of a range of unsaturated organic compounds under lower temperature and pressure conditions than conditions associated with industrial hydrogenation and hydrosilylation.
Claims23
A method of catalyzing a hydrogenation or hydrosilyation reaction comprising:
- reacting a organic substrate having at least one unsaturated group in the presence of a reducing agent with a 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 2 or greater;
- 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;
- R1, R2, R3 may also be linked to give cyclic systems;
- and
- wherein the M to R3PN− ratio is 1:1.
A method of catalyzing a hydrogenation or hydrosilylation reaction comprising:
- producing a catalyst by reduction of a compound of Formula IV:
- [M(NPR3)X(m-1)]n Formula IV
- where:
- m=2 or 3;
- n=2 to 4;
- the M to R3PN− ratio is 1:1;
- M is a first row transition metal selected from the group consisting of Co, Fe and Ni;
- X− can be any halide or pseudohalide;
- 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
- R1, R2, R3 substituents may also be linked by aliphatic hydrocarbyl groups to give cyclic systems [(e.g., R1/R2=—(CH2)n—, where n=3-10];
- and
- wherein the reducing agent used for the reduction of the complexes of Formula IV selected from the group of Li, Na, Na(Hg), Na-naphthalenide and K;
- and
- using the catalyst directly from the reduction reaction without subject to purification to catalyze the hydrogenation or hydrosilylation of a substrate having at least one unsaturated bond.
A method of catalyzing the hydrogenation or hydrosilylation of an organic compound having at least one unsaturated group 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 process for hydrogenation of an organic substrate having at least one unsaturated group:
- (i) combining the said organic substrate with a transition metal catalyst and a reductant to obtain a reaction medium;
- (ii) allowing the catalyst to catalyze the hydrogenation of the substrate;
- (iii) obtaining the reduced products from the organic substrate;
- wherein the organic substrate is a compound containing at least one unsaturated group;
- wherein the ratio of catalyst to substrate is less than 1:1;
- and
- wherein the catalyst has the formula:
- [M(NPR3)]n
- where
- n is a whole number of 2 or greater;
- 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 or an inert functional group containing at least one heteroatom selected from the group consisting of a Group 14, Group 15 and Group 16 element;
- and wherein R1, R2, R3 may also be linked by aliphatic groups to give cyclic systems.
Dependencies are inferred from the claim text.