US4504371A
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Process for the photocatalytic isomerization of olefins utilizing a mixed metal cluster
Assignee: Standard Oil Co
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Filing: 1984-02-13
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Granted: 1985-03-12
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Expires: 2004-02-13
Abstract
Abstract A novel process for the isomerization of olefins which employs a photocatalytic mixed metal cluster, wherein a solution of the olefin and the cluster is irradiated causing the cluster to become catalytically active and to isomerize the olefin. The photocatalytic mixed metal cluster has the empirical formula: (C.sub.n R.sub.n ').sub.a Fe.sub.b M.sub.c (CO).sub.d L.sub.e wherein n is five; wherein R' is selected from the group consisting of hydrogen, methyl, ethyl, acetyl, formyl, bromine, chlorine and fluorine; wherein M is a transition metal other than iron selected from the group consisting of Mo, Ru, Rh, Sc, Ti, V, Cr, Mn, Co, Ni, Cu and Zn; wherein L is a Group V type ligand; and further wherein a is from about one to five, b and c are from about one to five and b plus c is between two and six, d is from about five to 18 with the proviso that d is always equal to or greater than b plus c, and e is from about 0 to 18. A second novel process for the isomerization of olefins also employs a photocatalytic mixed metal cluster and irradiation wherein the cluster is first irradiated causing it to become catalytically active, and is then combined with an olefin to form a complex allowing the olefin to be isomerized.
Inventors
- 👤 Larry M. Cirjak
- 👤 Lynne Sutherland
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 12:13
CPC Classifications
B; B01; B01J; B01J31/00; B01J31/16; B01J31/22; B01J31/2282; B01J31/2291; B01J19/00; B01J19/08; B01J19/12; B01J19/121; B01J19/122; B01J19/123; B01J31/18; B01J31/1845; B01J31/1895; B01J31/20; B01J31/2295; B01J31/24; B01J31/2404; C; C07; C07C; C07C5/00; C07C5/22; C07C5/2206; C07C5/2266; C07C5/2286; C07C5/2293; C07C5/23; C07C5/25; C07C5/2506; C07C5/2562; C07C5/2593; B01J2531/00; B01J2531/02; B01J2531/0202; B01J2531/0211; B01J2531/10; B01J2531/16; B01J2531/20; B01J2531/26; B01J2531/30; B01J2531/35; B01J2531/40; B01J2531/46; B01J2531/50; B01J2531/56; B01J2531/60; B01J2531/62; B01J2531/64; B01J2531/70; B01J2531/72; B01J2531/80; B01J2531/82; B01J2531/821; B01J2531/822; B01J2531/84; B01J2531/842; C07C2531/00; C07C2531/16; C07C2531/22; C07C2531/24; Y; Y10; Y10S; Y10S204/00; Y10S204/90
Claims Analysis
Total Claims: 28
Claim 1
Independent Claim
118 words
A process for the isomerization of olefins comprising the steps of: forming a solution which comprises: an olefin; and, a photocatalytic mixed metal cluster, said cluster having the empirical formula (C.sub.n R.sub.n ').sub.a Fe.sub.b M.sub.c (CO).sub.d L.sub.e wherein n is five; wherein R' is selected from the group consisting of hydrogen, methyl, ethyl, acetyl, formyl, bromine, chlorine and fluorine; wherein M is a transition metal other than iron; wherein L is a Group V type ligand; and wherein a=1 to 5 b=1 to 5 c=1 to 5 b+c=2 to 6 d=5 to 18 with the proviso that d is always equal to or greater than b+c, and e=0 to 18; irradiating said solution and allowing isomerization to occur.
Claim 2
Dependent Claim
118 words
A process for the isomerization of olefins comprising the steps of: forming a solution which comprises: an olefin; and, a photocatalytic mixed metal cluster, said cluster having the empirical formula (C.sub.n R.sub.n ').sub.a Fe.sub.b M.sub.c (CO).sub.d L.sub.e wherein n is five; wherein R' is selected from the group consisting of hydrogen, methyl, ethyl, acetyl, formyl, bromine, chlorine and fluorine; wherein M is a transition metal other than iron; wherein L is a Group V type ligand; and wherein a=1 to 5 b=1 to 5 c=1 to 5 b+c=2 to 6 d=5 to 18 with the proviso that d is always equal to or greater than b+c, and e=0 to 18; irradiating said solution and allowing isomerization to occur.
Claim 3
Dependent Claim
38 words
The process of claim 1, wherein the olefin has at least four carbon atoms and has the formula ##STR4## wherein R 1 to R 5 are selected from the group consisting of hydrogen, alkyl, hydroxyl, alkenyl and phenyl.
Claim 4
Dependent Claim
20 words
The process of claim 2, wherein said olefin is selected from the group consisting of 1-pentene, cyclohexene, 1,3-cyclohexadiene and 1,5,9-cyclododecatriene.
Claim 5
Dependent Claim
14 words
The process of claim 1, wherein R' is hydrogen to yield a cyclopentadienyl ligand.
Claim 6
Dependent Claim
30 words
The process of claim 1, wherein said transition metal, M, is selected from the group consisting of Mo, Ru, Rh, Sc, Ti, V, Cr, Mn, Co, Ni, Cu and Zn.
Claim 7
Dependent Claim
12 words
The process of claim 5, wherein said transition metal, M, is Co.
Claim 8
Dependent Claim
12 words
The process of claim 5, wherein said transition metal, M, is Ni.
Claim 9
Dependent Claim
78 words
The process of claim 1, wherein said Group V type ligand, L, has the formula selected from the group consisting of XH 3 , R"XH 2 , R 2 "XH and R 3 "X; wherein X is selected from the group consisting of P, As and Sb; and, wherein R" is selected from the group consisting of methyl, ethyl, phenyl, tert-butyl, ortho-tolyl and oxy-compounds thereof wherein said X group and said R" group are separated by an oxygen.
Claim 10
Dependent Claim
21 words
The process of claim 1, wherein said photocatalytic mixed metal cluster is (C 5 H 5 )CoFe 2 (CO) 9 .
Claim 11
Dependent Claim
25 words
The process of claim 1 wherein said photocatalytic mixed metal cluster is (C 5 H 5 ) 2 Ni 2 Fe 2 (CO) 7 .
Claim 12
Dependent Claim
18 words
The process of claim 1, wherein said irradiation has an intensity of from about 220 to 1400 nm.
Claim 13
Dependent Claim
14 words
The process of claim 11, wherein said irradiation is provided for by a laser.
Claim 14
Dependent Claim
16 words
The process of claim 11, wherein said irradiation is a mercury lamp with a monochromatic filter.
Claim 15
Dependent Claim
124 words
A process for the isomerization of olefins comprising the steps of: irradiating a photocatalytic mixed metal cluster, said cluster having the empirical formula (C.sub.n R.sub.n ').sub.a Fe.sub.b M.sub.c (CO).sub.d L.sub.e wherein n is five; wherein R' is selected from the group consisting of hydrogen, methyl, ethyl, acetyl, formyl, bromine, chlorine and fluorine; wherein M is a transition metal other than iron; wherein L is a Group V type ligand; and wherein a=1 to 5 b=1 to 5 c=1 to 5 b+c=2 to 6 d=5 to 18 with the proviso that d is always equal to or greater than b+c; and e=0 to 18; combining said irradiated mixed metal cluster with an olefin to form a complex and allowing isomerization of the olefin to occur.
Claim 16
Dependent Claim
124 words
A process for the isomerization of olefins comprising the steps of: irradiating a photocatalytic mixed metal cluster, said cluster having the empirical formula (C.sub.n R.sub.n ').sub.a Fe.sub.b M.sub.c (CO).sub.d L.sub.e wherein n is five; wherein R' is selected from the group consisting of hydrogen, methyl, ethyl, acetyl, formyl, bromine, chlorine and fluorine; wherein M is a transition metal other than iron; wherein L is a Group V type ligand; and wherein a=1 to 5 b=1 to 5 c=1 to 5 b+c=2 to 6 d=5 to 18 with the proviso that d is always equal to or greater than b+c; and e=0 to 18; combining said irradiated mixed metal cluster with an olefin to form a complex and allowing isomerization of the olefin to occur.
Claim 17
Dependent Claim
38 words
The process of claim 14, wherein the olefin has at least four carbon atoms and has the formula ##STR5## wherein R 1 to R 5 are selected from the group consisting of hydrogen, alkyl, hydroxyl, alkenyl and phenyl.
Claim 18
Dependent Claim
20 words
The process of claim 15, wherein said olefin is selected from the group consisting of 1-pentene, cyclohexene, 1,3-cyclohexadiene and 1,5,9-cyclododecatriene.
Claim 19
Dependent Claim
14 words
The process of claim 14, wherein R' is hydrogen to yield a cyclopentadienyl ligand.
Claim 20
Dependent Claim
30 words
The process of claim 14, wherein said transition metal, M, is selected from the group consisting of Mo, Ru, Rh, Sc, Ti, V, Cr, Mn, Co, Ni, Cu and Zn.
Claim 21
Dependent Claim
12 words
The process of claim 18, wherein said transition metal, M, is Co.
Claim 22
Dependent Claim
12 words
The process of claim 18, wherein said transition metal, M, is Ni.
Claim 23
Dependent Claim
78 words
The process of claim 14, wherein said Group V type ligand, L, has the formula selected from the group consisting of XH 3 , R"XH 2 , R 2 "XH and R 3 "X; wherein X is selected from the group consisting of P, As and Sb; and, wherein R" is selected from the group consisting of methyl, ethyl, phenyl, tert-butyl, ortho-tolyl and oxy-compounds thereof wherein said X group and said R" group are separated by an oxygen.
Claim 24
Dependent Claim
21 words
The process of claim 14, wherein said photocatalytic mixed metal cluster is (C 5 H 5 )CoFe 2 (CO) 9 .
Claim 25
Dependent Claim
25 words
The process of claim 14, wherein said photocatalytic mixed metal cluster is (C 5 H 5 ) 2 Ni 2 Fe 2 (CO) 7 .
Claim 26
Dependent Claim
18 words
The process of claim 14, wherein said irradiation has an intensity of from about 220 to 1400 nm.
Claim 27
Dependent Claim
14 words
The process of claim 24, wherein said irradiation is provided for by a laser.
Claim 28
Dependent Claim
16 words
The process of claim 24, wherein said irradiation is a mercury lamp with a monochromatic filter.
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