IP Library Granted Patent US 9,308,525
Granted Patent B2
US 9,308,525 · App. 14/192,856 · Granted Apr 12, 2016

Methods for providing bond activation catalysts and related catalysts, systems, and methods

Inventors: William A. Goddard, III (Pasadena, CA); Mu-Jeng Cheng (Pasadena, CA); Ross Fu (Pasadena, CA)
Assignee: CALIFORNIA INSTITUTE OF TECHNOLOGY
B01J27/198B01J23/002B01J23/6482B01J23/6525B01J27/02B01J27/0576B01J27/19C07C253/24B01J2523/00
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Quick Facts
Patent No.
US 9,308,525
App. No.
14/192,856
Granted
Apr 12, 2016
Kind
B2
Abstract

Described herein are catalysts for activation of an R—H bond in a R—H substrate and related catalytic matrices, compositions, methods and systems.

Claims (29)

1. A catalytic matrix for activation of a R—H bond in a R—H substrate wherein R is an alkyl group, the R—H bond having an R—H bond enthalpy, the catalytic matrix comprising a plurality of catalytic cores of Formula (III):

wherein:

Y1 is NH, Y1 being capable of forming a Y1-H single bond with the H from the R—H substrate, and the Y1-H single bond having a Y1-H enthalpy;

X is P;

Z is NH;

Y2 is NH;

M is V;

i is 1-2;

j is 0-1; and

k is 0-1;

wherein Y1, X, Z, M, and Y2 are selected such that the Y1-H single bond enthalpy is equal or lower than the R—H single bond enthalpy;

and wherein the M and X of each catalytic core of the plurality of the catalytic cores of Formula (III) are connected to a supporting moiety A, wherein the supporting moiety A links the M and the X of each catalytic core of the plurality of the catalytic cores of Formula (III), the supporting moiety A configured to form a framework presenting Y1 of each catalytic core of the plurality of the catalytic cores for reaction with a substrate R—H

wherein A is a moiety of formula (IV):

in which:

 is an αand/or βbond;

M′ is V;

Y1 is NH;

Y2 is NH;

Z is NH; and

X* is P,

and wherein n is 1-6, and j, i2, and k2 are independently 0 or 1, and wherein a terminal Z of the moiety of Formula IV is linked to an M or an X element of a catalytic core of Formula III.

2. The catalytic matrix of claim 1 , wherein the matrix comprises at least 5% of a first catalytic core, at least 30-50% of a second catalytic core, at least 45-65% of a third catalytic core.

3. The catalytic matrix of claim 1 , wherein the framework comprises a plurality of layers, each layer of the plurality of layer presenting one or more catalytic cores configured to activate one or more R—H substrate.

4. The catalytic matrix of claim 3 , wherein each layer of the plurality of layers presents between 0.1 and 10% of a first catalytic core, between 10 and 50% of a second catalytic core, at least 40% of a third catalytic core.

5. The catalytic matrix of claim 1 , wherein at least 50% of the M and X of A and the catalytic core are bonded to =Y2 and =Y1groups, respectively.

6. The catalytic matrix of claim 1 , wherein the catalytic matrix comprises layers each comprising a plurality of groups of formula (III) having different values for i, j and/or k.

7. The catalytic matrix of claim 1 , wherein a difference between the Y1-H bond enthalpy and the R—H bond enthalpy is less than a threshold value in a model system.

8. The catalytic matrix of claim 1 , wherein the catalytic matrix comprises layers each comprising a pluralities of groups of formula (IV) having different values of j, i2 and k2.

9. The catalytic matrix of claim 8 , wherein the threshold value is between about 10 and 25 kcal/mol.

Assignments (2)
CONFIRMATORY LICENSE Recorded Nov 4, 2021
From: CALIFORNIA INSTITUTE OF TECHNOLOGY
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 058220/0024 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 5, 2014
From: GODDARD, WILLIAM A., III; CHENG, MU-JENG; FU, ROSS
To: CALIFORNIA INSTITUTE OF TECHNOLOGY
Reel/Frame 032823/0445 →
Continuity (2)
Provisional Application 61770216 · Feb 27, 2013
Related Publication 20140243545A1 · Aug 28, 2014