US3903120A
Expired / Lapsed
US
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Preparation of zerovalent nickel complexes from elemental nickel
Assignee: EIDP Inc
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Filing: 1973-12-13
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Granted: 1975-09-02
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Expires: 1993-12-13
Abstract
Abstract Zerovalent nickel complexes of the types Ni(MZ3)4 and Ni(MZ3)2A; wherein M is P, As or Sb, Z is R or OR, R is an alkyl or aryl radical having up to 18 carbon atoms and may be the same or different, and at least one Z is OR, A is a monoolefinic compound having 2 to 20 carbon atoms, the R radicals of a given MZ3 of Ni(MZ3)2A preferably being so chosen that the ligand has a cone angle of at least 130*; are prepared by reacting elemental nickel with the MZ3 ligand at a temperature in the range of 0*C.-150*C. in the presence of a halogen containing derivative of MZ3 as a catalyst. A more rapid reaction is realized by carrying out the preparation in an organonitrile solvent.
Inventors
- 👤 Jr Howard E Shook
- 👤 John B Thompson
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 00:45
CPC Classifications
C; C07; C07F; C07F15/00; C07F15/04
Claims Analysis
Total Claims: 15
Claim 1
Independent Claim
216 words
A PROCESS FOR THE PREPARATION OF A ZEROVALENT NICKEL COMPLEX OF THE GROUP CONSISTING OF NI(MZ3)4 AND NI(MZ3)2A WHEREIN M IS OF THE GROUP CONSISTING OF P AS AND SB Z IS R OR OR R IS AN ALKYL OR ARYL RADICAL UP TO 18 CARBON ATOMS AT LEAST ONE Z IS OR AND THE R RADICALS OF A GIVEN MZ3 MAY BE THE SAME OR DIFFERENT WHEREIN A IS A MONOOLEFINIC ORGANIC COMPOUND WITH NO OTHER CARBON-CARBON UNSATURATION AND HAVING FROM 2 TO 20 CARBON ATOMS, WHICH COMPRISES REACTING ELEMENTAL NICKEL WITH A LIGAND MZZ WHEREIN M AND Z ARE AS DEFINED ABOVE AT A TEMPERATURE IN THE RANGE OF 0*C-150*C IN THE PRESENCE OF AT LEAST 5 MOLES PER MILLION MOLES, BASED ON AMOUNT OF THE LIGAND, OF A CATALYST COMPOUND OF THE FORMULA (R''O)XR"YMXZ WHEREIN M IS DEFINED AS ABOVE R'' AND R" ARE ALKYL OR ARYL RADICALS HAVING UP TO 18 CARBON ATOMS AND MAY BE THE SAME OR DIFFERENT, WHEREIN X AND Z HAVE A VALUE OF 1-2 Y IS O OR 1 THE SUM OF X, Y AND Z IS 3 AND X IS A HALIDE OF THE GROUP CONSISTING OF -CI-B AND -1 AND WHEREIN FOR THE PREPARATION OF NI(MZ3)2A THERE IS ALSO PRESENT A MONOOLEFINIC ORGANIC COMPOUND A.
Claim 2
Dependent Claim
216 words
A PROCESS FOR THE PREPARATION OF A ZEROVALENT NICKEL COMPLEX OF THE GROUP CONSISTING OF NI(MZ3)4 AND NI(MZ3)2A WHEREIN M IS OF THE GROUP CONSISTING OF P AS AND SB Z IS R OR OR R IS AN ALKYL OR ARYL RADICAL UP TO 18 CARBON ATOMS AT LEAST ONE Z IS OR AND THE R RADICALS OF A GIVEN MZ3 MAY BE THE SAME OR DIFFERENT WHEREIN A IS A MONOOLEFINIC ORGANIC COMPOUND WITH NO OTHER CARBON-CARBON UNSATURATION AND HAVING FROM 2 TO 20 CARBON ATOMS, WHICH COMPRISES REACTING ELEMENTAL NICKEL WITH A LIGAND MZZ WHEREIN M AND Z ARE AS DEFINED ABOVE AT A TEMPERATURE IN THE RANGE OF 0*C-150*C IN THE PRESENCE OF AT LEAST 5 MOLES PER MILLION MOLES, BASED ON AMOUNT OF THE LIGAND, OF A CATALYST COMPOUND OF THE FORMULA (R''O)XR"YMXZ WHEREIN M IS DEFINED AS ABOVE R'' AND R" ARE ALKYL OR ARYL RADICALS HAVING UP TO 18 CARBON ATOMS AND MAY BE THE SAME OR DIFFERENT, WHEREIN X AND Z HAVE A VALUE OF 1-2 Y IS O OR 1 THE SUM OF X, Y AND Z IS 3 AND X IS A HALIDE OF THE GROUP CONSISTING OF -CI-B AND -1 AND WHEREIN FOR THE PREPARATION OF NI(MZ3)2A THERE IS ALSO PRESENT A MONOOLEFINIC ORGANIC COMPOUND A.
Claim 3
Dependent Claim
27 words
The process of claim 1 wherein the reaction is carried out at a temperature in the range of 25*-100*C. and in the added presence of an organonitrile.
Claim 4
Dependent Claim
15 words
The process of claim 2 wherein the zerovalent nickel complex is of the formula Ni(PZ3)4.
Claim 5
Dependent Claim
11 words
The process of claim 3 wherein PZ3 is a triaryl phosphite.
Claim 6
Dependent Claim
26 words
The process of claim 4 wherein the triaryl phosphite is of the group consisting of triphenyl phosphite, tri-p-tolyl phosphite, tri-m-tolyl phosphite and tri(m & p-tolyl) phosphite.
Claim 7
Dependent Claim
67 words
The process of claim 2 wherein the catalyst compound (R''O)xR''''yMXz is prepared in situ by introducing into the reaction mixture an initiator, the initiator being of the group consisting of halides of P, As and Sb, alkyl substituted halide of P, As and Sb, a halide of a metal, elemental halogen of the group consisting of Cl2, Br2 and I2 and their corresponding hydrogen and thionyl halides.
Claim 8
Dependent Claim
30 words
The process of Claim 6 wherein the initiator is of the group consisting of PX3, TiX4, ZrX4, HfX4 and HX wherein X is a -Cl, -Br or -I, and I2.
Claim 9
Dependent Claim
52 words
The process of claim 2 wherein the zerovalent nickel complex has the formula Ni(PZ3)2A, wherein the R radicals are so chosen that for a given PZ3 the cone angle is at least 130* and wherein A is a monoolefinic compound with no other carbon-carbon unsaturated having from 2 to 20 carbon atoms.
Claim 10
Dependent Claim
24 words
The process of claim 8 wherein A is a monoolefinic organic compound with a strong electronegative group conjugated with the olefin carbon-carbon double bond.
Claim 11
Dependent Claim
21 words
The process of claim 9 wherein the monoolefinic organic compound is of the group consisting of maleic anhydride, acrylonitrile and fumaronitrile.
Claim 12
Dependent Claim
22 words
The process of claim 10 wherein PZ3 is of the group consisting of tri-o-tolyl phosphite, tri-o-phenylphenyl phosphite, tri-2,5-xylyl phosphite and tri-2,4-xylyl phosphite.
Claim 13
Dependent Claim
42 words
The process of claim 11 wherein the catalyst compound (R''O)xR''''yMXz is prepared in situ by introducing into the reaction mixture an initiator of the group consisting of PX3, TiX4, ZrX4, HfX4 and HX wherein X is -Cl, -Br or -I and I2.
Claim 14
Dependent Claim
24 words
The process of claim 3 wherein the R radicals of a given PZ3 are different and at least one R is an o-tolyl radical.
Claim 15
Dependent Claim
23 words
The process of claim 13 wherein the R radicals other than o-tolyl are of the group consisting of phenyl, m-tolyl and p-tolyl radicals.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1978-09-01 | 1979-03-03 | 1979-09-02 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1982-09-01 | 1983-03-03 | 1983-09-02 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1986-09-01 | 1987-03-03 | 1987-09-02 | $7700.00 | Window Closed / Lapsed |