Functionalization of organic molecules using metal-organic frameworks (MOFS) as catalysts
The disclosure provides for catalytic multivariate metal organic frameworks and methods of use thereof.
1. A method to convert an alkane to an alcohol or carboxylic acid by contacting the alkane with a catalytically active heterogeneous vanadium containing metal organic framework (MOF) in the presence of an oxidant, wherein the vanadium containing MOF comprises a plurality of repeating cores comprising vanadium or vanadium ion(s) that are linked together by organic linking moieties.
2. The method of claim 1 , wherein the alkane is a linear (C 1 -C 12 )alkane.
3. The method of claim 1 , wherein the method is carried out in the presence of CO.
4. The method of claim 1 , wherein the oxidant is K 2 S 2 O 8 .
5. The method of claim 1 , wherein the alkane is converted to a carboxylic acid.
6. The method of claim 1 , wherein the vanadium ion(s) is selected from the group consisting of V 5+ , V 4+ , V 3+ , and V 2+ .
7. The method of claim 1 , wherein the metal organic framework comprises vanadium or vanadium ions with octahedral coordination spheres.
8. The method of claim 1 , wherein the metal organic framework has a linking moiety with a parent chain selected from the group consisting of hydrocarbon, hetero-alkane, hetero-alkene, hetero-alkyne, and heterocycle; and wherein the parent chain is functionalized with at least one linking cluster.
9. The method of claim 1 , wherein the metal organic framework is generated from a plurality of linking moieties comprising one or more of structural Formulae I, II, III, IV, V, VI, VII, VIII, IX and X:
wherein:
R 1 -R 4 , R 16 -R 20 , R 23 -R 30 , R 38 -R 96 are independently selected from the group consisting of H, functional group (FG), (C 1 -C 20 )alkyl, substituted (C 1 -C 20 )alkenyl, substituted (C 1 -C 20 )alkenyl, (C 1 -C 20 )alkynyl, substituted (C 1 -C 20 )alkynyl, hetero-(C 1 -C 20 )alkyl, substituted hetero-(C 1 -C 20 )alkyl, hetero-(C 1 -C 20 )alkenyl, substituted hetero-(C 1 -C 20 )alkenyl, hetero-(C 1 -C 20 )alkynyl, substituted hetero-(C 1 -C 20 )alkynyl, (C 1 -C 20 )cycloalkyl, substituted (C 1 -C 20 )cycloalkyl, aryl, substituted aryl, heterocycle, substituted heterocycle, —C(R 5 ) 3 , —CH(R 5 ) 2 , —CH 2 R 5 , —C(R 6 ) 3 , —CH(R 6 ) 2 , —CH 2 R 6 , —OC(R 5 ) 3 , —OCH(R 5 ) 2 , —OCH 2 R 5 , —OC(R 6 ) 3 , —OCH(R 6 ) 2 , —OCH 2 R 6 , and
wherein R 1 and R 3 may be linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle, wherein R 2 and R 4 may be linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle, wherein R 18 and R 19 may be linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle, wherein R 24 and R 25 may be linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle, and/or wherein R 28 and R 29 may be linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle;
R 5 is selected from the group consisting of FG, (C 1 -C 20 )alkyl, (C 1 -C 20 )substituted alkyl, (C 1 -C 20 )alkenyl, substituted (C 1 -C 20 )alkenyl, (C 1 -C 20 )alkynyl, substituted (C 1 -C 20 )alkynyl, hetero-(C 1 -C 20 )alkyl, substituted hetero-(C 1 -C 20 )alkyl, hetero-(C 1 -C 20 )alkenyl, substituted hetero-(C 1 -C 20 )alkenyl, hetero-(C 1 -C 20 )alkynyl, substituted hetero-(C 1 -C 20 )alkynyl, hemiacetal, hemiketal, acetal, ketal, and orthoester;
R 6 is one or more substituted or unsubstituted rings selected from the group consisting of cycloalkyl, aryl, and heterocycle;
Z is either a C or N; and
X is a number from 0 to 10.
10. The method of claim 1 , wherein the metal organic framework is generated from a plurality of linking moieties comprising structural Formula I, II, III, IV, V, VI, VII, VIII, IX or X:
wherein:
R 1 -R 4 , R 15 -R 20 , R 23 -R 30 , R 38 -R 96 are independently selected from the group consisting of H, functional group (FG), (C 1 -C 20 )alkyl, substituted (C 1 -C 20 )alkyl, (C 1 -C 20 )alkenyl, substituted (C 1 -C 20 )alkenyl, (C 1 -C 20 )alkynyl, substituted (C 1 -C 20 )alkynyl, hetero-(C 1 -C 20 )alkyl, substituted hetero-(C 1 -C 20 )alkyl, hetero-(C 1 -C 20 )alkenyl, substituted hetero-(C 1 -C 20 )alkenyl, hetero-(C 1 -C 20 )alkynyl, substituted hetero-(C 1 -C 20 )alkynyl, (C 1 -C 20 )cycloalkyl, substituted (C 1 -C 20 )cycloalkyl, aryl, substituted aryl, heterocycle, substituted heterocycle, —C(R 5 ) 3 , —CH(R 5 ) 2 , —CH 2 R 5 , —C(R 6 ) 3 , —CH(R 6 ) 2 , —CH 2 R 6 , —OC(R 5 ) 3 , —OCH(R 5 ) 2 , —OCH 2 R 5 , —OC(R 6 ) 3 , —OCH(R 6 ) 2 , —OCH 2 R 6 , and
wherein R 1 and R 3 may be linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle, wherein R 2 and R 4 may be linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle, wherein R 18 and R 19 may be linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle, wherein R 24 and R 25 may be linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle, and/or wherein R 28 and R 29 may be linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle;
R 5 is selected from the group consisting of FG, (C 1 -C 20 )alkyl, (C 1 -C 20 )substituted alkyl, (C 1 -C 20 )alkenyl, substituted (C 1 -C 20 )alkenyl, (C 1 -C 20 )alkynyl, substituted (C 1 -C 20 )alkynyl, hetero-(C 1 -C 20 )alkyl, substituted hetero-(C 1 -C 20 )alkyl, hetero-(C 1 -C 20 )alkenyl, substituted hetero-(C 1 -C 20 )alkenyl, hetero-(C 1 -C 20 )alkynyl, substituted hetero-(C 1 -C 20 )alkynyl, hemiacetal, hemiketal, acetal, ketal, and orthoester;
R 6 is one or more substituted or unsubstituted rings selected from the group consisting of cycloalkyl, aryl, and heterocycle;
Z is either a C or N; and
X is a number from 0 to 10.
11. The method of claim 1 , wherein the metal organic framework is generated from a plurality of linking moieties comprising one or more of structural Formulae I, II, III, IV, V, VI, VII, and VIII:
wherein:
R 1 -R 4 , R 15 -R 20 , R 23 -R 30 , R 38 -R 88 are independently selected from the group consisting of H, functional group (FG), (C 1 -C 6 )alkyl, substituted (C 1 -C 6 )alkyl, (C 1 -C 6 )alkenyl, substituted (C 1 -C 6 )alkenyl, (C 1 -C 6 )alkynyl, substituted (C 1 -C 6 )alkynyl, hetero-(C 1 -C 6 )alkyl, substituted hetero-(C 1 -C 6 )alkyl, hetero-(C 1 -C 6 )alkenyl, substituted hetero-(C 1 -C 6 )alkenyl, hetero-(C 1 -C 6 )alkynyl, substituted hetero-(C 1 -C 6 )alkynyl, (C 1 -C 6 )cycloalkyl, substituted (C 1 -C 6 )cycloalkyl, aryl, substituted aryl, heterocycle, substituted heterocycle, —C(R 5 ) 3 , —CH(R 5 ) 2 , —CH 2 R 5 , —C(R 6 ) 3 , —CH(R 6 ) 2 , —CH 2 R 6 , —OC(R 5 ) 3 , —OCH(R 5 ) 2 , —OCH 2 R 5 , —OC(R 6 ) 3 , —OCH(R 6 ) 2 , —OCH 2 R 6 , and
wherein R 1 and R 3 may be linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle, wherein R 2 and R 4 may be linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle, wherein R 18 and R 16 may be linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle, wherein R 24 and R 25 may be linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle, and/or wherein R 28 and R 29 may be linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle;
R 5 is selected from the group consisting of FG, (C 1 -C 6 )alkyl, (C 1 -C 6 )substituted alkyl, (C 1 -C 6 )alkenyl, substituted (C 1 -C 6 )alkenyl, (C 1 -C 6 )alkynyl, substituted (C 1 -C 6 )alkynyl, hetero-(C 1 -C 6 )alkyl, substituted hetero-(C 1 -C 6 )alkyl, hetero-(C 1 -C 6 )alkenyl, substituted hetero-(C 1 -C 6 )alkenyl, hetero-(C 1 -C 6 )alkynyl, substituted hetero-(C 1 -C 6 )alkynyl, hemiacetal, hemiketal, acetal, ketal, and orthoester;
R 6 is one or more substituted or unsubstituted rings selected from the group consisting of cycloalkyl, aryl, and heterocycle; and
X is a number from 0 to 3.
12. The method of claim 1 , wherein the metal organic framework is generated from a plurality of linking moieties comprising one or more of structural Formulae I, II, III, IV, V, VI, VII, and VIII:
wherein:
R 1 -R 4 , R 15 -R 20 , R 23 -R 30 , R 38 -R 88 are independently selected from the group consisting of H, functional group (FG), (C 1 -C 6 )alkyl, substituted (C 1 -C 6 )alkyl, (C 1 -C 6 )alkenyl, substituted (C 1 -C 6 )alkenyl, (C 1 -C 6 )alkynyl, substituted (C 1 -C 6 )alkynyl, hetero-(C 1 -C 6 )alkyl, substituted hetero-(C 1 -C 6 )alkyl, hetero-(C 1 -C 6 )alkenyl, substituted hetero-(C 1 -C 6 )alkenyl, hetero-(C 1 -C 6 )alkynyl, substituted hetero-(C 1 -C 6 )alkynyl, (C 1 -C 6 )cycloalkyl, substituted (C 1 -C 6 )cycloalkyl, aryl, substituted aryl, heterocycle, substituted heterocycle, —C(R 5 ) 3 , —CH(R 5 ) 2 , —CH 2 R 5 , —C(R 6 ) 3 , —CH(R 6 ) 2 , —CH 2 R 6 , —OC(R 5 ) 3 , —OCH(R 5 ) 2 , —OCH 2 R 5 , —OC(R 6 ) 3 , —OCH(R 6 ) 2 , —OCH 2 R 6 , and
wherein R 1 and R 3 may be linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle, wherein R 2 and R 4 may be linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle, wherein R 18 and R 19 may be linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle, wherein R 24 and R 25 may be linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle, and/or wherein R 28 and R 29 may be linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle;
R 5 is selected from the group consisting of FG, (C 1 -C 6 )alkyl, (C 1 -C 6 )substituted alkyl, (C 1 -C 6 )alkenyl, substituted (C 1 -C 6 )alkenyl, (C 1 -C 6 )alkynyl, substituted (C 1 -C 6 )alkynyl, hetero-(C 1 -C 6 )alkyl, substituted hetero-(C 1 -C 6 )alkyl, hetero-(C 1 -C 6 )alkenyl, substituted hetero-(C 1 -C 6 )alkenyl, hetero-(C 1 -C 6 )alkynyl, substituted hetero-(C 1 -C 6 )alkynyl, hemiacetal, hemiketal, acetal, ketal, and orthoester;
R 6 is one or more substituted or unsubstituted rings selected from the group consisting of cycloalkyl, aryl, and heterocycle; and
X is a number from 0 to 3.
13. The method of claim 1 , wherein the metal organic framework is generated from a linking moiety comprising structural Formula I:
wherein:
R 1 -R 4 are independently selected from the group consisting of H, halo, amine, cyano, Si(OH) 3 , Ge(OH) 3 , Sn(OH) 3 , Si(SH) 4 , Ge(SH) 4 , AsO 3 H, AsO 4 H, P(SH) 3 , As(SH) 3 , CO 2 H, CS 2 H, NO 2 , SO 3 H, Si(OH) 3 , Ge(OH) 3 , Sn(OH) 3 , Si(SH) 4 , Ge(SH) 4 , Sn(SH) 4 , POSH, AsO 3 H, AsO 4 H, P(SH) 3 , As(SH) 3 , (C 1 -C 6 )alkyl, substituted (C 1 -C 6 )alkyl, (C 1 -C 6 )alkenyl, substituted (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, substituted (C 2 -C 6 )alkynyl, hetero-(C 1 -C 6 )alkyl, substituted hetero-(C 1 -C 6 )alkyl, hetero-(C 1 -C 6 )alkenyl, substituted hetero-(C 2 -C 6 )alkenyl, hetero-(C 2 -C 6 )alkynyl, substituted hetero-(C 2 -C 6 )alkynyl, aryl, substituted aryl, heterocycle, substituted heterocycle, —C(R 5 ) 3 , —CH(R 5 ) 2 , —CH 2 R 5 , —C(R 6 ) 3 , —CH(R 6 ) 2 , —CH 2 R 6 , —OC(R 5 ) 3 , —OCH(R 5 ) 2 , —OCH 2 R 5 , —OC(R 6 ) 3 , —OCH(R 6 ) 2 , —OCH 2 R 6 ,
wherein R 1 and R 3 may be linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle, and/or wherein R 2 and R 4 may be linked together to form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, aryl and heterocycle;
R 5 is selected from the group comprising hydroxyl, amine, thiol, cyano, carboxyl, (C 1 -C 6 )alkyl, (C 1 -C 6 )substituted alkyl, (C 1 -C 6 )alkenyl, substituted (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, substituted (C 2 -C 6 )alkynyl, hetero-(C 1 -C 6 )alkyl, substituted hetero-(C 1 -C 6 )alkyl, hetero-(C 1 -C 6 )alkenyl, substituted hetero-(C 2 -C 6 )alkenyl, hetero-(C 2 -C 6 )alkynyl, substituted hetero-(C 2 -C 6 )alkynyl, hemiacetal, hemiketal, acetal, ketal, and orthoester;
R 6 is one or more substituted or unsubstituted rings selected from the group consisting of cycloalkyl, aryl, and heterocycle; and
X is a number from 0 to 3.
14. The method of claim 13 , wherein the linking moiety is selected from the group consisting of
15. The method of claim 1 , wherein at least one of the functional groups of the metal organic framework is further modified, substituted, or eliminated with a different functional group post-synthesis of the framework.
16. The method of claim 15 , wherein the metal organic framework is further modified by adding a functional group post synthesis of the framework that has one or more properties selected from the group consisting of: binds a metal ion, increases the hydrophobicity of the framework, modifies the gas sorption of the framework, modifies the pore size of the framework, and tethers a catalyst to the framework.
17. The method of claim 1 , wherein the metal organic framework comprises [V(O)(C 10 H 8 O 4 )] or [V(O)(C 8 H 4 O 4 )].
18. The method of claim 1 , wherein the alkane is either methane or ethane.
19. The method of claim 1 , wherein the method converts methane to acetic acid with up to a 70% yield.
20. The method of claim 1 , wherein the method can be performed multiple times with the same MOF.