- Synthesis and reactivity of phosphine-arenesulfonate palladium(II) alkyl complexes that contain methoxy substituents
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Phosphine-arenesulfonate ligands that contain 1-3 methoxy substituents on the benzo linker, P(2-OMe-Ph)2(2-SO3Na-5-OMe-Ph) (Na[1a]), P(2-MeO-Ph)2(2-SO3Na-4,5-(OMe)2-Ph) (Na[1b]) and P(2-MeO-Ph)2
- Liu, Qian,Jordan, Richard F.
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p. 207 - 214
(2019/06/24)
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- TETRAMERISATION OF ETHYLENE
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A process for the tetramerisation of ethylene includes contacting ethylene with a catalyst under ethylene oligomerisation conditions. The catalyst comprises a source of chromium, a ligating compound, and an activator. The ligating compound includes a phosphine that forms part of a cyclic structure.
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Page/Page column 31
(2014/12/09)
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- Ligand effects in chromium diphosphine catalysed olefin co-trimerisation and diene trimerisation
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A series of symmetric and unsymmetric N,N-bis(diarylphosphino)amine ('PNP') ligands (Ar2PN(R)PNAr′2: R = Me, Ar2 = o-anisyl, Ar′2 = Ph, 1, R = Me, Ar2 = o-tolyl, Ar′2 = Ph, 2, R = Me, Ar2 = Ph(o-ethyl), Ar′2 = Ph, 3, R = Me, Ar2 = Ar′2 = o-anisyl, 4, R = iPr, Ar2 = Ar′2 = Ph, 5) and symmetric N,N′-bis(diarylphosphino)dimethylhydrazine ('PNNP') ligands (Ar2PN(Me)N(Me)PAr2: Ar2 = o-tolyl, 6, Ar 2 = o-anisyl, 7) have been synthesised. Catalytic screening for ethene/styrene co-trimerisation and isoprene trimerisation was performed via the in situ complexation to [CrCl3(THF)3] followed by activation with methylaluminoxane (MAO). PNNP catalytic systems showed a significant increase in activity and selectivity over previously reported PNP systems in isoprene trimerisation. Comparing the symmetric and unsymmetric variants in ethene and styrene co-trimerisation resulted in a switch in selectivity, an unsymmetric catalytic (o-anisyl)2PN(Me)PPh 2 (1) ligand system affording unique incorporation of two styrenic monomers into the co-trimer product distribution differing from the familiar two ethene and one styrene ω-substituted alkenes. Complexes of the type [(diphosphine)Cr(CO)4] 8-11 were also synthesised, the single-crystal X-ray diffraction of which are reported. We propose the mechanisms of these catalytic transformations and an insight into the effect of the ligand series on the chromacyclic catalytic intermediates. The Royal Society of Chemistry.
- Bowen, Lucy E.,Charernsuk, Manutsavin,Hey, Thomas W.,McMullin, Claire L.,Orpen, A. Guy,Wass, Duncan F.
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experimental part
p. 560 - 567
(2010/04/03)
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- ETHYLENE TRIMERIZATION CATALYSTS COMPRISING P-N-P LIGANDS AND THEIR USE
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A new P-N-P ligand having the general formula (Ph1)(Ph2)P-N-P(Ph3)(Ph4) R2 wherein each Of Ph1, Ph2, Ph3 and Ph4 is a phenyl group bonded to a phosphorus gr
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Page/Page column 19
(2010/04/27)
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- LIGANDS AND CATALYST SYSTEMS THEREOF FOR THE CATALYTIC OLIGOMERIZATION OF OLEFINIC MONOMERS
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The present invention relates to a ligand having the general Formula (I); P(R4J-P(R1) (R2)=N(R3) (I) wherein: the R1 group is selected from a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl group; the R2 group is selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl groups; the R3 is selected from hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a heterohydrocarbyl group, a substituted heterohydrocarbyl group, a silyl group or derivative thereof; the R4 group is an optionally substituted alkylenedioxy, alkylenedimercapto or alkylenediamino structure which is bound to the phosphorus atom through the two oxygen, sulphur or nitrogen atoms of the alkylenedioxy, alkylenedimercapto or alkylenediamino structure or an optionally substituted arylenedioxy, arylenedimercapto or arylenediamino structure which is bound to the phosphorus atom through the two oxygen, sulphur or nitrogen atoms of the arylenedioxy, arylenedimercapto or arylenediamino structure.
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Page/Page column 51-52
(2008/12/06)
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- LIGANDS AND CATALYST SYSTEMS FOR THE OLIGOMERIZATION OF OLEFINIC MONOMERS
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The present invention relates to a ligand having the general formula (I) : (R1) 2P-P(R1)m(R2)n=N(R3) (I) wherein R3 is selected from hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a heterohydrocarbyl group, a substituted heterohydrocarbyl group, a silyl group or derivative thereof; the R1 groups are independently selected from an optionally substituted aromatic group bearing a polar substituent on at least one of the ortho-positions; and the R2 groups are independently selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl groups with the proviso that when the group is aromatic it does not contain a polar substituent at any of the ortho-positions, with the proviso that m is 0 or 1, n is 1 or 2 and the total of m + n is 2. The present invention also relates to catalyst systems and a process for the simultaneous trimerization and tetramerization of olefinic monomers using said ligands.
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Page/Page column 41
(2008/12/06)
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- POLYMERISATION PROCESS CATALYSED BY A BIDENTATE BISPHOSPHINE-GROUP VIII METAL COMPLEX
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A process for the polymerization and copolymerization of olefins is disclosed, comprising contacting the monomeric olefin under polymerization conditions with a polymerization catalyst or catalyst system which comprises (a) a source of a Group VIII metal; (b) a bidentate phosphine ligand having the formula (R1)(R1)P-X-P(R1)(R1), where each R1 is independently selected from a phenyl group or a substitued phenyl group with the proviso that at least one of the R1 groups is a phenyl group having at least one ortho substituent, and X is a bridging group of the structure -[N]x-[P]y-[N]- where x and y are independently 0 or 1, or -C(R4)2- where R4 may be the same or different and is hydrogen or a monovavlent hydrocarbyl, substituted hydrocarbyl or hetero-hydrocarbyl group; and optionally (c) a promoter.
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Page/Page column 10
(2010/11/27)
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- Copolymerization of ethylene and alkyl vinyl ethers by a (Phosphinesulfonate)PdMe catalyst
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The neutral complex (PO-OMe)PdMe(py) (1, PO-OMe = 2-[bis(2-OMe-Ph)phosphino]-4-methylbenzenesulfonate) polymerizes ethylene to a linear polymer with 1-10 branches/103 carbons (mostly methyl) and vinyl and 2-olefin unsaturated end groups. Complex 1 copolymerizes ethylene and alkyl vinyl ethers (CH2=CHOR, 2a-c: R = tBu (a), Et (b), Bu (c)) in toluene at 60-100 °C to linear copolymers containing up to 7 mol % of vinyl ether. Addition of CH2=CHOR lowers the polymerization rate and the polymer molecular weight. The copolymer structures are similar to that of homopolyethylene generated under the same conditions. The major comonomer units are -CH2CH(OR)CH2- (I) and CH3CH(OR)CH2- (II). The ethylene/CH2CHOR copolymers can be converted to hydroxy- and bromo-polyethylene. The results of control experiments argue against cationic and radical mechanisms for the copolymerization, and an insertion mechanism is proposed. The reaction of base-free (PO-OMe)PdMe with CH2CHOEt yields the adduct (PO-OMe)PdMe(CH2=CHOEt), which undergoes 1,2-insertion to generate (PO-OMe)PdCH2CH(OEt)Me. Copyright
- Luo, Shuji,Vela, Javier,Liet, Graham R.,Jordan, Richard F.
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p. 8946 - 8947
(2008/02/09)
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- CATALYTIC OLIGOMERIZATION OF OLEFINIC MONOMERS
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A catalyst precursor composition comprising: a) a source of chromium, molybdenum or tungsten; b) a first ligand having the general formula (I); [in-line-formulae](R1)(R2)P—X—P(R3)(R4)??(I) [/in-line-formulae] wherein: X is a bridging group of the formula —N(R5)—, wherein R5 is selected from hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a heterohydrocarbyl group, a substituted heterohydrocarbyl group, a silyl group or derivative thereof; at least three of R1 to R4 are independently selected from optionally substituted aromatic groups, each bearing a polar substituent on at least one of the ortho-positions; and optionally one of R1 to R4 is independently selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl groups with the proviso that when the group is aromatic it does not contain a polar substituent at any of the ortho-positions; c) a second ligand having the general formula (II); [in-line-formulae](R1′)(R2′)P—X′—P(R3′)(R4′)??(II) [/in-line-formulae] wherein: X′ is a bridging group as defined for X of the first ligand, component (b), of general formula (I); at least R1′ and R2′ of R1′ to R4′ are independently selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl groups with the proviso that when the group is aromatic it does not contain a polar substituent at any of the ortho-positions; and optionally none, one or both of R3′ and R4′ are independently selected from an optionally substituted aromatic group bearing a polar substituent on at least one of the ortho-positions. The present invention also relates to a catalyst system comprising the catalyst precursor composition of the present invention and additional component; d) a cocatalyst. The present invention further relates to a process for the trimerization and tetramerization of olefinic monomers, particularly the trimerization and tetramerization of ethylene to 1-hexene and 1-octene, wherein the process comprises contacting at least one olefinic monomer with the catalyst system of the present invention.
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Page/Page column 12
(2008/06/13)
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- CATALYTIC PROCESS FOR THE OLIGOMERIZATION OF OLEFINIC MONOMERS
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A process for the simultaneous trimerization and tetramerization of olefinic monomers , wherein the process comprises contacting at least one olefinic monomer with catalyst system comprising : a) a source of chromium, molybdenum or tungsten; b) a ligand having the general formula (I) ; (R1)2P-X-P (R1)m(R2)n wherein : X is a bridging group of the formula -N(R3)-, wherein R3 is selected from hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a heterohydrocarbyl group, a substituted heterohydrocarbyl group, a silyl group or derivative thereof; the R1 groups are independently selected from an optionally substituted aromatic group bearing a polar substituent on at least one of the ortho-positions; and the R2 groups are independently selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl groups and c) a cocatalyst, at a pressure in the range of from below atmospheric to about 40 barg and at a temperature in the range of from about 0 °C to about 120 °C. The present invention further relates to a process for the simultaneous trimerization and tetramerization of ethylene to 1-hexene and 1-octene.
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Page/Page column 38-39
(2010/11/27)
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- ROLE OF THROUGH-SPACE 2p-3d OVERLAP EFFECTS IN LITHIUM-ION CATALYZED WITTIG REACTIONS
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The reactions of benzylidene-bis-(o-methoxyphenyl)methylphosphorane (17) with either benzaldehyde or trimethylacetaldehyde in the presence of lithium ion in tetrahydrofuran solution give higher ratios of cis:trans alkenes than do the corresponding reactions with benzylidenediphenylmethylphosphorane (16).However, when the intermediate oxaphosphetanes, 11 and 22 are produced by the action of lithium diphenylphosphide and lithium bis-(o-methoxyphenyl)phosphide (5), respectively, on trans-stilbene oxide (6), with subsequent addition of methyl iodide, the reactions are stereospecific, and on;y cis-stilbene is produced in each case.The results themselves and also attempted crossover experiments indicate that the oxephosphetanes do not revert to ylide plus aldehyde in the presence of lithium ion.The above observations, when combined with our knowledge of the preferred geometry of the through space 2p-3d overlap effect have enabled us to suggest a detailed mechanism for the lithium ion-catalyzed Wittig reaction of benzylidene-bis-(o-methoxyphenyl)methylphosphorane (17) with an aldehyde.
- McEwen, W. E.,Beaver, B. D.
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p. 259 - 273
(2007/10/02)
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