Organosilicon on solid oxides, and related complexes, compositions, methods and systems

Patent metadata

Field	Value
Publication number	US-11512102-B2
Application number	US-201916563681-A
Country	US
Kind code	B2
Filing date	Sep 6, 2019
Priority date	Sep 6, 2018
Publication date	Nov 29, 2022
Grant date	Nov 29, 2022

Abstract

Organosilicon Lewis acids supported on activated oxides and metal oxo complexes grafted on the organosilicon Lewis acids as heterogeneous catalysts and the related compositions, methods and systems are described. These organosilicon Lewis acids and the grafted metal oxo complexes catalyze industrially important chemical reactions including, respectively, C—F bond activation and olefin metathesis reactions such as homocoupling and polymerizations.

First claim

The invention claimed is:

1. A solid organosilicon compound comprising a Formula (I)
[M 1 m O o1 Si 1 (R 1 R 2 R 3 )L q/z ] [M 2 O o2 Si 2 (R 1 R 2 R 3 )] x   (I)

wherein
M 1 and M 2 are selected from the group consisting of Al, Zn, and Zr, and any combinations thereof-having an oxidation state of +p, wherein p ranges from 2 to 4,
Si 1 is a Lewis acidic silicon connected to M 1 via an oxygen, wherein other atoms in the solid organosilicon compound are represented stoichiometrically in relation to Si 1 ,
q represents a charge for M 1 m O o1 Si 1 (R 1 R 2 R 3 ), wherein q ranges from 1 to 3,
L is selected from the group consisting of sulfate (SO 4 2− ), sulfite (SO 3 2− ), selenate (SeO 4 2− ), phosphonate (HPO 3 2− ), phosphate (PO 4 3− ), pyrophosphate (P 2 O 7 4− ), chloride (Cl − ), chlorate (ClO 3− ), bromide (Br), bromate (BrO 3 − ), tetraborate (B 4 O 7 2− ), vanadate (VO 4 3− ), tungstate (WO 4 2− ), molybdate (MoO 4 2− ), p-toluene sulfonate, trifluoroacetate and any combinations thereof and has a negative charge of −z, wherein z ranges from 1 to 3,
Si 2 represents a silicon bounded to M 2 via an oxygen,
m is number of M 1 ,
o1, and o2 are the number of O respectively bonded to M 1 and M 2 ,
wherein (m×p)+[o1×(−2)]+1= q,

q/z is the number of counter anion L,
p +[ o 2×(−2)]+1=0,

R 1 , R 2 , and R 3 are each independent a substituent comprising 1 to 24 carbon atoms,
x ranges from 0 to 1000.

2. The solid organosilicon compound of claim 1 , wherein M 1 and M 2 are Zr.

3. The solid organosilicon compound of claim 1 , wherein L is sulfate (SO 4 2− ).

4. The solid organosilicon compound of claim 1 , wherein x ranges from 0.05 to 10.

5. The solid organosilicon compound of claim 1 , wherein m ranges from 10 to 1000.

6. The solid organosilicon compound of claim 1 , wherein
M 1 and M 2 are Zr having an oxidation state of +4,
L is a sulfate anion bounded to M 1 ,
Si 2 is at least two atoms spaced apart from an oxygen of the sulfate anion,
m ranges from 10 to 1000,
x ranges from 0.05 to 10.

7. A catalytic system for hydrodefluorination (HDF) of a fluorocarbon compound, the catalytic system comprising
a solid organosilicon compound of Formula (I) as defined in claim 1 ,
a fluorocarbon compound and
a silane compound comprising at least one Si—H group.

8. The solid organosilicon compound of claim 1 , wherein:
M 1 and M 2 are each Zr,
q is 2,
p is 4,
L is sulfate (SO 4 2− ),
m is 100,
o1 is 399/2 and o2 is 5/2,
R 1 , R 2 , and R 3 are each independent isopropyl, and
x is 10.

9. The catalytic system for hydrodefluorination (HDF) of claim 7 , wherein the fluorocarbon includes at least one sp 3 C—F bond.

10. The catalytic system for hydrodefluorination (HDF) of claims 7 , wherein the fluorocarbon is represented by Formula (XI)
C n H 2n+2−s F s   (XI)

wherein
n ranges from 1 to 30, and
s ranges from 1 to 2n.

11. The catalytic system for hydrodefluorination (HDF) of claim 7 , wherein the fluorocarbon is benzotrifluoride, octofluorotoluene, or 1-fluoroadamatane.

12. The catalytic system for hydrodefluorination (HDF) of claim 7 , wherein the fluorocarbon is represented by Formula (XII)
R″ F   (XII)

wherein
R″ is selected from the group consisting of a linear C1-C15 alkyl; branched linear C3-C15 alkyl; cyclic C3-C15 alkyl; linear, cyclic, or branched C2-C15 alkenyl; linear, cyclic, or branched C2-C15 alkynyl; C6-C20 substituted or unsubstituted aryl; and C6-C20 substituted or unsubstituted heteroaryl group.

13. The catalytic system of any 7 , wherein the silane compound is selected from the group consisting of triethylsilane, diethylmethylsilane, polymethylhydrosilane (PMHS), methyldiethoxysilane, diethoxydimethylsilane triethoxysilane.

14. A method for hydrodefluorination (HDF) of a fluorocarbon compound, the method comprises
contacting a solid organosilicon compound of Formula (I) as defined in claim 1 with the fluorocarbon compound,
the contacting performed in presence of a silane compound comprising at least one Si—H group for a time and under condition to allow hydrodefluorination of the fluorocarbon compound.

15. A method for preparing a solid organosilicon compound of Formula (I) as defined in claim 1 , the method comprises contacting a solid oxide of Formula (IV)
[M 1 m HO o1 L q/z ][M 2 HO o2 ] x   (IV)

with a silane of Formula (V)
SiR 1 R 2 R 3 R 4   (V)

wherein
M 1 and M 2 are an element having an oxidation state of +p,
L is a counter anion bounded to M 1 and has a negative charge of −z,
m is number of M 1 ,
o1, and o2 the number of O respectively bonded to M 1 and M 2 ,
( m×p )+[ o 1×(−2)]+1= q,

q/z is the number of counter anion L,
p +[ o 2×(−2)]+1=0,

R 1 , R 2 , R 3 , and R 4 are each independent a substituent comprising 1 to 24 carbon atoms, an isopropyl, an allyl group, a chloride, a bromide, an iodide, or a triflate,
x ranges from 0 to 1000

for a time and under condition to form an organosilicon compound Formula (I).

16. The method of claim 15 , wherein
M 1 and M 2 are Mo having an oxidation state of +4,
L is a sulfate anion bounded to M 1 and has a negative charge of −2,
R 1 , R 2 , and R 3 are each isopropyl group.

Assignees

• Univ California

Inventors

• Conley Matthew P
• Culver Damien B

Classifications

• C07F7/0836 Primary

  Compounds with one or more Si-OH or Si-O-metal linkage · CPC title

• B01J2531/31

  Aluminium · CPC title

• B01J2531/26

  Zinc · CPC title

• C07C6/04

  at a carbon-to-carbon double bond · CPC title

• C07C1/26

  starting from organic compounds containing only halogen atoms as hetero-atoms · CPC title