US4298541A
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Trihydrocarbyl silyl-substituted alkyl diaryl phosphine transition metal complexes and their use as homogeneous catalysts
Assignee: ExxonMobil Technology and Engineering Co
•
Filing: 1979-02-12
•
Granted: 1981-11-03
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Expires: 1999-02-12
Abstract
Abstract Novel homogeneous trihydrocarbyl silyl-substituted alkyl diaryl phosphine transition metal complexes of the general formula: [(Ar2PQ)ySiR4-y]g(MXn)s wherein Ar is a C6 to C10 aromatic hydrocarbyl radical, Q is a C1 to C30 saturated straight chain divalent radical either unsubstituted or substituted, R is an unsubstituted C1 to C10 hydrocarbyl, C1 to C10 monosubstituted hydrocarbyl, phenyl radical, y is 1 to 4, g times y is 1 to 6, M is a transition metal selected from the group consisting of Group VIII transition metals, X is an anion or organic ligand excluding halogen satisfying the coordination sites of the metal, n is 2 to 6 and s is 1 to 3, are disclosed. These materials are superior catalysts for the selective hydroformylation of olefins, particularly in the presence of excess quantities of the ligand of the formula: [(Ar2P)[Q]ySiR4-y] wherein Ar, Q, R, and y are as previously defined.
Inventors
- 👤 Alexis A. Oswald
- 👤 Torris G. Jermansen
- 👤 Andrew A. Westner
- 👤 I-Der Huang
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 09:48
CPC Classifications
B; B01; B01J; B01J31/00; B01J31/16; B01J31/1608; B01J31/24; B01J31/2404; C; C07; C07C; C07C45/00; C07C45/49; C07C45/50; B01J2231/00; B01J2231/30; B01J2231/32; B01J2231/321; B01J2531/00; B01J2531/80; B01J2531/82; B01J2531/821; B01J2531/822; B01J2531/827; B01J2531/84; B01J2531/845
Claims Analysis
Total Claims: 38
Claim 1
Independent Claim
145 words
Complexes of the formula: [(Ar.sub.2 PQ).sub.y SiR.sub.4-y ].sub.g (MX.sub.n).sub.s wherein Ar is selected from phenyl and mono-, di- or trisubstituted phenyl, said substituents being selected from the group consisting of fluorine, methyl and acetyl; Q is selected from xylylene and a C 2 -C 14 straight chain alkylene divalent radical; R is a C 1 to C 6 hydrocarbyl radical selected from the group consisting of C 1 to C 6 alkyl, C 5 and C 6 cycloalkyl, and phenyl; M is a Group VIII transition metal selected from the group consisting of Co, Rh, Ir, Ru,; X is an anion or organic ligand, excluding halogen, satisfying the coordination sites of the metal; y is 1 to 4; g is 1 to 6 with the proviso that g times y is 1 to 6; n is 2 to 6; and s is 1 to 3.
Claim 2
Dependent Claim
145 words
Complexes of the formula: [(Ar.sub.2 PQ).sub.y SiR.sub.4-y ].sub.g (MX.sub.n).sub.s wherein Ar is selected from phenyl and mono-, di- or trisubstituted phenyl, said substituents being selected from the group consisting of fluorine, methyl and acetyl; Q is selected from xylylene and a C 2 -C 14 straight chain alkylene divalent radical; R is a C 1 to C 6 hydrocarbyl radical selected from the group consisting of C 1 to C 6 alkyl, C 5 and C 6 cycloalkyl, and phenyl; M is a Group VIII transition metal selected from the group consisting of Co, Rh, Ir, Ru,; X is an anion or organic ligand, excluding halogen, satisfying the coordination sites of the metal; y is 1 to 4; g is 1 to 6 with the proviso that g times y is 1 to 6; n is 2 to 6; and s is 1 to 3.
Claim 3
Dependent Claim
8 words
Complexes of claim 1, wherein M is Rh.
Claim 4
Dependent Claim
8 words
Complexes of claim 2, wherein Ar is phenyl.
Claim 5
Dependent Claim
99 words
Complexes of the formula [(Ar.sub.2 PQ).sub.y SiR.sub.4-y ].sub.g [Rh(CO)H].sub.s wherein Ar is selected from phenyl and mono-, di- or tri-substituted phenyl, said substituents being selected from the group consisting of fluorine, methyl and acetyl; Q is selected from a xylylene and C 2 to C 14 straight chain alkylene divalent radical; R is a C 1 to C 6 hydrocarbyl radical selected from the group consisting of C 1 to C 6 alkyl, C 5 and C 6 cycloalkyl, and phenyl; y is 1 to 4; g times y is 1 to 6; and s is 1 to 3.
Claim 6
Dependent Claim
99 words
Complexes of the formula [(Ar.sub.2 PQ).sub.y SiR.sub.4-y ].sub.g [Rh(CO)H].sub.s wherein Ar is selected from phenyl and mono-, di- or tri-substituted phenyl, said substituents being selected from the group consisting of fluorine, methyl and acetyl; Q is selected from a xylylene and C 2 to C 14 straight chain alkylene divalent radical; R is a C 1 to C 6 hydrocarbyl radical selected from the group consisting of C 1 to C 6 alkyl, C 5 and C 6 cycloalkyl, and phenyl; y is 1 to 4; g times y is 1 to 6; and s is 1 to 3.
Claim 7
Dependent Claim
79 words
Complexes of the formula (Ar.sub.2 PQSiR.sub.3).sub.3 Rh(CO)H wherein Ar is selected from phenyl and mono-, di- or tri-substituted phenyl, said substituents being selected from the group consisting of methyl, fluorine and acetyl; Q is selected from xylylene and a C 2 to C 14 straight chain alkylene divalent radical; and R is C 1 to C 6 hydrocarbyl radical selected from the group consisting of C 1 to C 6 alkyl, C 5 and C 6 cycloalkyl, and phenyl.
Claim 8
Dependent Claim
79 words
Complexes of the formula (Ar.sub.2 PQSiR.sub.3).sub.3 Rh(CO)H wherein Ar is selected from phenyl and mono-, di- or tri-substituted phenyl, said substituents being selected from the group consisting of methyl, fluorine and acetyl; Q is selected from xylylene and a C 2 to C 14 straight chain alkylene divalent radical; and R is C 1 to C 6 hydrocarbyl radical selected from the group consisting of C 1 to C 6 alkyl, C 5 and C 6 cycloalkyl, and phenyl.
Claim 9
Dependent Claim
10 words
Complexes of claim 4 or 5 wherein, Ar is phenyl.
Claim 10
Dependent Claim
84 words
Complexes of the formula [(Ar.sub.2 PQSiR.sub.3).sub.2 Rh(CO).sub.3 ].sup.+ [B(C.sub.6 H.sub.5).sub.4 ].sup.- wherein Ar is selected from phenyl and mono-, di- or tri-substituted phenyl, said substituents being selected from the group consisting of fluorine, methyl and acetyl; Q is selected from a xylylene and a C 2 to C 14 straight chain alkylene divalent radical; and R is a C 1 to C 6 hydrocarbyl radical selected from the group of C 1 to C 6 alkyl, C 5 and C 6 cycloalkyl, and phenyl.
Claim 11
Dependent Claim
84 words
Complexes of the formula [(Ar.sub.2 PQSiR.sub.3).sub.2 Rh(CO).sub.3 ].sup.+ [B(C.sub.6 H.sub.5).sub.4 ].sup.- wherein Ar is selected from phenyl and mono-, di- or tri-substituted phenyl, said substituents being selected from the group consisting of fluorine, methyl and acetyl; Q is selected from a xylylene and a C 2 to C 14 straight chain alkylene divalent radical; and R is a C 1 to C 6 hydrocarbyl radical selected from the group of C 1 to C 6 alkyl, C 5 and C 6 cycloalkyl, and phenyl.
Claim 12
Dependent Claim
8 words
Complexes of claim 7, wherein Ar is phenyl.
Claim 13
Dependent Claim
62 words
Complexes of the formula [(φ.sub.2 P(CH.sub.2).sub.m).sub.y SiR.sub.4-y ].sub.g [Rh(CO)H].sub.s wherein R is a C 1 to C 6 hydrocarbyl radical selected from the group of C 1 to C 6 alkyl, C 5 and C 6 cycloalkyl and phenyl; m is 2 to 14; y is 1 to 4; g times y is 1 to 6; and s is 1 to 3.
Claim 14
Dependent Claim
62 words
Complexes of the formula [(φ.sub.2 P(CH.sub.2).sub.m).sub.y SiR.sub.4-y ].sub.g [Rh(CO)H].sub.s wherein R is a C 1 to C 6 hydrocarbyl radical selected from the group of C 1 to C 6 alkyl, C 5 and C 6 cycloalkyl and phenyl; m is 2 to 14; y is 1 to 4; g times y is 1 to 6; and s is 1 to 3.
Claim 15
Dependent Claim
10 words
Complexes of claim 9, wherein y is 1 or 2.
Claim 16
Dependent Claim
17 words
Complexes of claim 10, wherein y is 2, g times y is 6 and s is 2.
Claim 17
Dependent Claim
15 words
Complexes of the formula ([φ.sub.2 P(CH.sub.2).sub.m ].sub.2 Si(CH.sub.3).sub.2).sub.3 [Rh(CO)H].sub.2 wherein m is 2 to 14.
Claim 18
Dependent Claim
15 words
Complexes of the formula ([φ.sub.2 P(CH.sub.2).sub.m ].sub.2 Si(CH.sub.3).sub.2).sub.3 [Rh(CO)H].sub.2 wherein m is 2 to 14.
Claim 19
Dependent Claim
10 words
Complexes of claim 12, wherein m is 2 to 3.
Claim 20
Dependent Claim
110 words
Complexes of the formula: [(Ar.sub.2 PQ).sub.y SiR.sub.4-y ].sub.g (MX.sub.n).sub.s wherein Ar is an unsubstituted C 6 -C 10 aromatic radical Q is an unsubstituted C 1 to C 30 saturated open chain alkylene radical; R is an unsubstituted C 1 to C 10 hydrocarbyl radical; M is a Group VIII transition metal selected from the group consisting of Co, Rh, Ir, Ru, X is an anion or organic ligand, excluding halogen, satisfying the coordination sites of the metal; y is 1 to 4; g is 1 to 6 with the proviso that g times y is 1 to 6; n is 2 to 6; and s is 1 to 3.
Claim 21
Dependent Claim
110 words
Complexes of the formula: [(Ar.sub.2 PQ).sub.y SiR.sub.4-y ].sub.g (MX.sub.n).sub.s wherein Ar is an unsubstituted C 6 -C 10 aromatic radical Q is an unsubstituted C 1 to C 30 saturated open chain alkylene radical; R is an unsubstituted C 1 to C 10 hydrocarbyl radical; M is a Group VIII transition metal selected from the group consisting of Co, Rh, Ir, Ru, X is an anion or organic ligand, excluding halogen, satisfying the coordination sites of the metal; y is 1 to 4; g is 1 to 6 with the proviso that g times y is 1 to 6; n is 2 to 6; and s is 1 to 3.
Claim 22
Dependent Claim
69 words
Complexes of the formula: [(Ar.sub.2 PQ).sub.y SiR.sub.4-y ].sub.g [Rh(CO)H].sub.2 wherein Ar is an unsubstituted C 6 to C 10 aromatic radical; Q is an unsubstituted C 1 to C 30 saturated open chain alkylene radical; R is an unsubstituted C 1 to C 10 hydrocarbyl radical; y is 1 to 4; g times y is 1 to 6; n is 2 to 6; and s is 1 to 3.
Claim 23
Dependent Claim
69 words
Complexes of the formula: [(Ar.sub.2 PQ).sub.y SiR.sub.4-y ].sub.g [Rh(CO)H].sub.2 wherein Ar is an unsubstituted C 6 to C 10 aromatic radical; Q is an unsubstituted C 1 to C 30 saturated open chain alkylene radical; R is an unsubstituted C 1 to C 10 hydrocarbyl radical; y is 1 to 4; g times y is 1 to 6; n is 2 to 6; and s is 1 to 3.
Claim 24
Dependent Claim
147 words
Complexes of the formula: [(Ar.sub.2 PQ).sub.y SiR.sub.4-y ].sub.g (MX.sub.n).sub.s wherein Ar is a substituted or unsubstituted C 6 -C 10 aromatic radical, Q is a substituted or unsubstituted C 1 to C 30 saturated open chain alkylene radical, R is an unsubstituted or monosubstituted C 1 to C 10 hydrocarbyl radical, M is a Group VIII transition metal, selected from the group consisting of Co, Rh, Ir, Ru, Fe or Os, X is an anion or organic ligand, excluding halogen, satisfying the coordination sites of the metal, y is 1 to 4, g is 1 to 6 with the proviso that g times y is 1 to 6, n is 2 to 6, and s is 1 to 3, said substituents on said aromatic radical, on said alkylene radical and on said hydrocarbyl radical being chemically unreactive with materials used in and the products of hydroformylation reaction.
Claim 25
Dependent Claim
147 words
Complexes of the formula: [(Ar.sub.2 PQ).sub.y SiR.sub.4-y ].sub.g (MX.sub.n).sub.s wherein Ar is a substituted or unsubstituted C 6 -C 10 aromatic radical, Q is a substituted or unsubstituted C 1 to C 30 saturated open chain alkylene radical, R is an unsubstituted or monosubstituted C 1 to C 10 hydrocarbyl radical, M is a Group VIII transition metal, selected from the group consisting of Co, Rh, Ir, Ru, Fe or Os, X is an anion or organic ligand, excluding halogen, satisfying the coordination sites of the metal, y is 1 to 4, g is 1 to 6 with the proviso that g times y is 1 to 6, n is 2 to 6, and s is 1 to 3, said substituents on said aromatic radical, on said alkylene radical and on said hydrocarbyl radical being chemically unreactive with materials used in and the products of hydroformylation reaction.
Claim 26
Dependent Claim
11 words
Complexes of claim 16 wherein M is Co, Rh, Ir, Ru.
Claim 27
Dependent Claim
18 words
Complexes of claim 17 wherein X is selected from the group consisting of H, CO and tertiary phosphine.
Claim 28
Dependent Claim
16 words
Complexes of claim 16 wherein s is 1, y is 1, g is 1 to 6.
Claim 29
Dependent Claim
31 words
Complexes of claim 19 wherein M is selected from the group consisting of Co, Rh, Ir and Ru; X is selected from the group consisting of H, CO, and tertiary phosphine.
Claim 30
Dependent Claim
79 words
Complexes of the formula (Ar.sub.2 PQSiR.sub.3).sub.3 RH(CO)H wherein Ar is a substituted or unsubstituted C 6 to C 10 aromatic radical, Q is an unsubstituted or monosubstituted C 1 to C 30 open chain alkylene radical; and R is an unsubstituted or monosubstituted C 1 to C 10 hydrocarbyl radical, said substituents on said aromatic radical, on said alkylene radical and on said hydrocarbyl radical being chemically unreactive with materials used in and the products of a hydroformylation reaction.
Claim 31
Dependent Claim
79 words
Complexes of the formula (Ar.sub.2 PQSiR.sub.3).sub.3 RH(CO)H wherein Ar is a substituted or unsubstituted C 6 to C 10 aromatic radical, Q is an unsubstituted or monosubstituted C 1 to C 30 open chain alkylene radical; and R is an unsubstituted or monosubstituted C 1 to C 10 hydrocarbyl radical, said substituents on said aromatic radical, on said alkylene radical and on said hydrocarbyl radical being chemically unreactive with materials used in and the products of a hydroformylation reaction.
Claim 32
Dependent Claim
83 words
Complexes of the formula [Ar.sub.2 PQSiR.sub.3).sub.2 Rh(CO).sub.3 ].sup.+ [B(C.sub.6 H.sub.5).sub.4 ].sup.- wherein Ar is a substituted or unsubstituted C 6 to C 10 aromatic radical, Q is a substituted or unsubstituted C 1 to C 30 open chain alkylene radical, and R is an unsubstituted or monosubstituted C 1 to C 10 hydrocarbyl radical, said substituents on said aromatic radical, on said alkylene radical and on said hydrocarbyl radical being chemically unreactive with materials used in and the products of a hydroformylation reaction.
Claim 33
Dependent Claim
83 words
Complexes of the formula [Ar.sub.2 PQSiR.sub.3).sub.2 Rh(CO).sub.3 ].sup.+ [B(C.sub.6 H.sub.5).sub.4 ].sup.- wherein Ar is a substituted or unsubstituted C 6 to C 10 aromatic radical, Q is a substituted or unsubstituted C 1 to C 30 open chain alkylene radical, and R is an unsubstituted or monosubstituted C 1 to C 10 hydrocarbyl radical, said substituents on said aromatic radical, on said alkylene radical and on said hydrocarbyl radical being chemically unreactive with materials used in and the products of a hydroformylation reaction.
Claim 34
Dependent Claim
14 words
Complexes of the formula [φ.sub.2 P(CH.sub.2).sub.m Si(CH.sub.3).sub.3 ].sub.3.RH(CO)H wherein m is 1 to 4.
Claim 35
Dependent Claim
14 words
Complexes of the formula [φ.sub.2 P(CH.sub.2).sub.m Si(CH.sub.3).sub.3 ].sub.3.RH(CO)H wherein m is 1 to 4.
Claim 36
Dependent Claim
11 words
The complex of claim 23 wherein m is 2 or 3.
Claim 37
Dependent Claim
10 words
A complex of the formula [φ.sub.2 PCH.sub.2 CH.sub.2 Si(CH.sub.3).sub.3 ].sub.3.Rh(CO)H.
Claim 38
Dependent Claim
10 words
A complex of the formula [φ.sub.2 PCH.sub.2 CH.sub.2 Si(CH.sub.3).sub.3 ].sub.3.Rh(CO)H.
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