NOVEL CATALYST COMPOSITION

Abstract: A catalyst composition prepared by reacting together (a) a source of a Group VIII metal; (b) a bidentate phosphine ligand having a t least two phosphorus atoms joined by a bridging group of the formula -(N)x-(P)y-N- where x is 0 or 1 and y is 0 or 1; and (c) a promoter is disclosed. The Group VIII metal is preferably palladium. The promoter can be a weakly or non-coordinating anion. Alternatively it can be a boron hydrocarbyl compound or an aluminoxane. Also disclosed are novel bidentate phosphine ligands and intermediates therefor as well as novel palladium complexes. The catalysts are used in the preparation of polyketones.

Description: NOVEL CATALYST COMPOSITION The present invention relates to a novel catalyst composition and to a process for the preparation of intei polymei s of olefins and cai bon monoxide by polymerising a mi iue of one oi mυi e olefins and cai bon monoxide in the presence of such catalyst compositions The preparation of lineai alternating intei polymei s of olefins and carbon monoxide havin Όg the formula - Q [(CR 2 - CR 2 ) n ] m where the R groups are independently hydrogen or hydiocaibyl groups, n is at least 1 and m is a large integer, is known fiom US 36944 12 Such linear alternating interpolymers, which hereinafter will be referred to as polyketones, are prepared accoiding to US 3694412 by polymeπsing a mixtui e of one or more olefins and carbon monoxide in the presence of palladium halide and an inert solvent However, the process descnbed in US 3694 12 is slow even at elevated temperature and pressure An improved version of the pi ocess described in US 3694412 is described in European patent applications 181014 and 121965 It was subsequently found that the l ate of the polymei isation piocess could be increased considerably by using a palladium catalyst with inter alia a bidentate phosphine and the anion of a cai boxyhc acid having a pKa of less than 2 (as measured m aqueous solution) Examples of anions which can be used include trichloroacetate, dichloroacetate, teti fluoi o-boiate, hexafluorophosphate p-toluene sulphonate, and borosalicylate such anions being l espectively the conjugate anions of tπchloroacetic acid, dichloroacetic acid teti afluoiobonc acid, hexafluorophosphoπc acid, p-toluenesulphonic acid and borosalicy c acid More recently the use of hydrocarbyl boranes as effective promoters in palladium catalysed polyketo e synthesis has been disclosed in EP 61 335 It has now been found that instead of using a bidentate phosphine as described in EP 121 65, catalyst systems, in particular palladium catalyst systems, based upon novel phosphine ligands can be employed According to the present invention, there is provided a catalyst composition prepared by reacting together (a) a source of a Group VIII metal, (b) a bidentate phosphine ligand having at least two phosphorus atoms joined by a bridging group of the formula -(N)χ - (P)y - N - where x is 0 or 1 and y is 0 or 1 , and (c) a promotei The present invention further provides a process foi preparing polyketones by polymerising a mixture of carbon monoxide and one oi more olefins in the presence of a catalyst composition as defined hereinabove The term polyketone is used herein to mean tin interpolymer of one or more olefins with carbon monoxide The idealised structuie of such a material would comprise a one, two or three dimensional netwoi k of stnctly alternating olefin and carbon monoxide units Although polyketones prepai d according to the present invention correspond to this idealised structuie, it is envisaged that materials corresponding to this structuie in the main but containing small regimes (ie up to 10 wt %) of the corresponding polyolefin also fall within the definition The catalyst composition described above is itself pi epared by reacting together (a) a source of Group Vlll metal, (b) a bidentate phosphine ligand having the formula as shown above, and (c) a pi omotei As regards component (a), this is a Gi oup Vl ll metal, the Group Vlll metals are iron, cobalt, nickel, ruthenium, i hodium, palladium, osmium, iridium and platinum The second row Group Vl ll metals (ie ruthenium, rhodium and palladium) are preferred, paiticularly preferred is palladium As regards component (b), this is a bidentate phosphine ligand having at least two phosphorus atoms joined by a budging gi oup of the foi mula -(NK-(P).-N- where each of the N atoms which may constitute pan oi all of the bridge between the said two phosphorus atoms ai e ti ivalent and the P atom that may constitute part of the bridge between the said two phosphorus atoms (i.e y= l ) is trivalent or pentavalent Where all the atoms in the bridge whether N or P are trivalent, two of the three bonds of each of the atoms that constitute the bridge are directed to adjacent atoms. The third bond can be directed to an adjacent atom in the bridge (to give a double bond in the bridge), but is more likely to be directed to a monovalent, preferably organic, group which is directly bonded to the respective bridge atom but which does not form part of the bridge itself Where y= l , the phosphorus atom forming part of the bridge may alternatively be pentavalent in which case two of the bonds are directed to the adjacent atoms to form part of the bridge The other three bonds can for example be directed to three monovalent groups or preferably to one monovalent group and a double bond for example to oxygen or sulphur The bridging group is likely to be of the formula - (NR 2 ) X - (PR 3 ) y - NR 2 - where each R 2 is the same or different and R 2 and R 3 represent a monovalent, preferably organic, group and x and y are independently 0 or 1. In particular component (b) can be a compound of formula 1: R l R l P - (NR 2 ) x - (PR 3 ) y - NR 2 - P ' / (I) R l ^ \ ! where R' may be the same or different and is an organic group, R 2 , R 3 , x and y are defined above R ' is an organic group and may be hydrocarbyl (for example aryl, alkyl), alkoxy, amido and substituted derivatives thereof Where R ' is alkyl, it is preferably a C \ to CO alkyl group, especially ethyl Where ' is aryl, it is for example phenyl or an aromatic group substituted at one or both ortho positions with respect to the phosphorus atoms with a polar substituent for example an alkoxy or an amido group for example a methoxy group for example o-anisyl preferably o-anisyl Where R ' is alkoxy, R ' may suitably be OC β H5 Where R 1 is NR 4 2 , R 4 may suitably be alkyl Alternatively more than one of the R 1 groups may be linked to form a cyclic structure in which case the two phosphorus atoms and the -(NX-(P) V -N- bridge would form part of such a cyclic structure. A particular example of this type of ligand would be cyclotetraphosphazeπes of the formula [NR 2 PR'], or compounds of the formula [N R 2 PR'N R NR PR ; N R 2 NR 2 PR'] where R 2 and f have the meanings given herein R and R are monovalent groups, preferably monovalent organic groups. 2 For example R can be hydrogen or a hydrocarbyl group, preferably a C] to CO alkyl group, for example methyl or ethyl or an aryl group preferably phenyl. R3 can be a hydrocarbyl group or substituted hydrocarbyl, preferably a C ] to Cg alkyl group. Alternatively, R 3 is an aryl group for example phenyl or substituted phenyl. Alternatively R 2 and/or R 1 can be a hetero group e.g. OR 5 , SR 5 or NR 6 2 where R 5 and R 6 are independently a hydrocarbyl group e.g. OMe, OEt, OPh, NMe 2 , NEt 2 etc. It is a feature of the hetero group that the group is bonded to the bridge atoms directly through a hetero atom. As regards x and y, these are independently 0 or I Preferably x and y are both 0 in which case component (b) comprises a PNP unit (Two phosphorus atoms with a single N atom as a bridge) The ligands can be prepared using procedures known to the man skilled in the art and disclosed in published literature Ligands of the formula (R')2PNR P(R') 2 (i e x=y=0) can be prepared by reacting 2 moles of R' P (halide) with NH 2 R 2 in the presence of a base (for example NR 3 ), R 2 'P (halide) is preferably R 2 'PCI A range of R 2 'PC1 are available commercially but can also be made by reacting R 2 NPCI 2 where R is a hydrocarbyl group for example Me or Et with LiR' or the corresponding Grignard reagent. R NPCI 2 can be obtained commercially or obtained by reacting NHR 2 and PC1 3 ln the case of R 2 'PCI where R 1 is o-anisyl, R 2 'PCI can be prepared by reacting a solution of o-anisyl lithium in THF/hexane with R 2 NPCI 2 where R is a hydrocarbyl group for example, Me, Et or isopropyl and treating the subsequent (o-anisyl) 2 PNR 2 with a Bronsted acid, preferably anhydrous HCl The advantage of using o- anisyl lithium (as opposed to the corresponding Grignard reagent) is that the final R 2 'PC1 product is easier to purify and extract Where R 1 is o-anisyl the reaction of R 2 1 P(halide) with NH 2 R 2 in the presence of a base to give (R') 2 PNR 2 P(R') 2 is preferably effected using methylamine i e R 2 =ιVle and preferably in dichloromethane It is also possible to react NH 2 R 2 with 1 mole of R 2 'P(halide) in the presence of base to generate RT ' PNHR 2 which can then be f ther reacted in the presence of base with one mole of R 2 ''P(halide) where R 1 ≠R 1 ' to give an unsymmetrical bisphosphine of the formula R2' 2 PR''2, for example where R'=phenyl, and R 1 ' = o-anisyl and 2 =n-butyl The compounds (o-anisyl)2P(halide) % its preparation and ligands of the formula (R') 2 P-(N) S -(P) V -N-P(R') 2 in particular (R') 2 PN(R) P(R') 2 where at least one of groups R 1 is an o-anisyl group and R is a hydrocarbyl group are novel and consequently form part of the present invention. Ligands where x= 1 y=0 i.e. having a bridging group of -N-N- can be prepared as described in Inorganic Chemistry 1 95 (34) 5483-5488. Ligands where x=l y= I i.e. having a bridging group of-N-P-N can be prepared as described in J.Chem Soc. (A) 1967 1492- 1498 and J.Chem Soc (A) 1970, 2715-2719. An alternative method of preparing R 2 'PC1 is to react PCI 3 with the corresponding R 1 Grignard reagent in THF followed by precipitation of magnesium halide by-product by adding dioxan The corresponding R^P RPR^ can be made by further reacting the product of the fu st step with H 2 NR in the presence of a base (e.g. NR- in THF. As regards component (c) which is a promoter, this can be a source of an anion which is either non-coordinating or weakly coordinating Such anions are suitably the conjugate bases of strong acids having eg a pKa of less than 6, preferably less than 2 (eg. HBF4, HPF , HSbFg, paratoluene sulphonic acid). Alternatively, the promoter can be a boron hydrocarbyl compound for example a boron alkyl, or boron aryl compound In particular the Boron hydrocarbyl compound can be a Lewis acid of the formula BXYZ where at least one of X, Y and Z is a monovalent hydrocarbyl group Where any one of X, Y or Z is a monovalent hydrocarbyl group, it is suitably an alkyl, for example a C \ to C alkyl group, or an aryl group for example a substituted or unsubstituted phenyl group for example C6H5 or C6F5 Other suitable monovalent hydrocarbyl groups are p-Hal C5 H 4 (where Hal = F, Cl, Br), m, m - C5 H 3 (CF 3 ) 2 , CF 3 and C2F5. It is to be understood that two or three of the groups X, Y and Z can together form bi or trivalent groups respectively At least one of X, Y and Z is a monovalent hydrocarbyl group, however it is preferred that at least two, preferably three of X, Y and Z are each monovalent hydrocarbyl groups Suitable examples of such Lewis acids are BMe , BEt 3 , B(C&H5) 3 , B[m,m - (CF^ b β H 3 ] 3 , B(mesityl)3, B(p-Hal C 6 H 4 ) 3 (where Hal - F, Cl, Ui ), B and B(C 6 F 5 ) 3 , preferably B( -HalC6H4) 3 , B(C (1 FN)- and B(C 0 F5) 3 Wheie one or more of X, Y and Z is not a hydrocarbyl group, it is suitably a OH, OR or halide group, preferably a halide group, fo example fluoride, chloride or bromide, especially fluoride Examples of compounds where one of X, Y, Z is a group other than a hydrocarbyl group are boronic acids of the formula RB(OH) 2 where R is a hydrocarbyl group eg PhB (OH) 2 and hydrocarbyl 1 ,3,2 - benzodioxaboroles Other suitable boron hydrocarbyl compounds for use in this invention are borate salts of the formula MBR4 where M is an alkali metal eg Li, Na and at least one of the groups R is a hydrocarbyl group (eg C H , C5F5 and substituted analogues) For example, a suitable compound could be LiB(C6F5)4 or aB(CόH5)4 Where one or more of the R groups is not a hydrocarbyl group it is suitably an OH, OR or halide group f r example OH A typical example of such a compound is NaBPf (OH) When a boron hydrocarbyl compound is used, for example a Lewis Acid BXYZ, it is added to the reaction medium in an amount such that the Group VIII metal boron ratio is in the range 10 I to I 200, preferably 1 1 to 1 100, most preferably I 5 to I 70 eg 1 50 The boron hydrocarbyl compound can be added in a single addition, preferably at the beginning of the polymerisation reaction, in several discrete additions throughout the l eaction oi continuously Alternativley the promotei could be anion containing a plurality of boron atoms such as those disclosed in EP 702045 A2 01 an aluminoxane Where the Group Vlll metal is palladium, the souice of palladium can include simple inorganic and 01 game salts, eg halides, nitrates, carboxylates and the like as well as organometallic and cooi d ation complexes In some cases, by suitable choice of coordination complex, it may be possible to add the palladium and the compound of foi mula 1 as a single entity ln addition to the bidentate phosphine ligand, the Group Vlll metal compound may preferably comprise othei gioups 01 ligands bonded to the Group VIII metal, these groups or ligands may or may not derive from any Group VIII metal precursors that have been used in generating the Group VIII metal compound. Such groups or ligands ate suitably halides, especially chloride, acetate, trifluoroacetate, tosylate, nitrate, sulphate, acetyl acetonate, cyanide, preferably acetate 01 labile ligands e g ti itluoi oacetate, tosylate, nitnles, solvent molecules e g water, acetone The Group Vll l metal compound can suitably be a neutral or cationic compound L 2 Pd(P-P) (11) 01 [L 2 ' Pd(P-P)](A)2 (HI) where each L is independently a monodentate ligand or L taken together is a bidentate ligand and P-P is a bidentate phosphine ligand having at least two phosphorus atoms joined by a bridging group of the formula -(N) x (P) y -N- as defined above for example -(NR 2 ) X - (PR ) y - NR 2 - where each R 2 is the same or different and is a hydrogen or hydrocarbyl group, R J is a hydrocarbyl group and x and y are independently 0 or 1. Alternatively R 2 and R " " can independently be hetero groups. In particular a compound of the formula I where R '< R 2 and R 3 have the meanings assigned to them as hereinabove, can be used as P-P. L is typically a halide or carboxylate, for example CH 3 COO or CF3COO. With regard to compounds of Formula 111, L ' is typically a neutral ligand such as, benzonitrile, acetonitrile, diethyl ether, or water. A is a weakly coordinating or non- coordinating anion as defined under component (c) above or (A) 2 together can be a weakly or non-coordinating dianion In a further aspect of the present invention there are provided compounds of formulae 11 or III as defined above provided that in the case of compounds of formula 11 when P-P is a bidentate ligand having at least two phosphorus atoms joined by a bridging group of the formula -(N) x -(P) y -N where x=0, y=0 (i.e. single nitrogen atom in the bridge), L is not Cl and when L is Cl, and PP is (R 7 ) 2 PN(Me)N(Me)P(R 7 ) 2 , R 7 is not alkoxy. Particular examples of compounds of formulae 11 and I II are [Pd { Ph 2 PN(N4e)N(Me)PPh2}CI 2 ] and [Pd{Ph 2 PN(Me)N(Me)PPh 2 }(PhCN) 2 ] [BF 4 ] 2 . Where the promoter is a non-coordinating or weakly coordinating anion, this can also be incorporated into a discrete compound as a counter anion as in compounds of Formula 111 Alternatively, the anion can be used in the form of a salt or its conjugate acid together with the Group Vlll metal and the compound of formula I whether the latter two are added as a single discrete compound or are added as two compounds. Although any source of the Group VII I metal can be used, it may be necessary when a metal complex having strongly coordinating ligands is employed, to ensure that such ligands are removed. An example of such a complex is palladium acetate where the acetate anions bind to the palladium In such cases the acetate anions can be removed by adding component (c) above as the conjugate acid of a non-coordinating or weakly coordinating anion since such a conjugate acid will protonate the acetate anions and cause their removal. Alternatively, when metal halides eg palladium halides are used it is preferred to use a thallium or silver salt of a non-coordinating or weakly coordinating anion In such cases a metathesis reaction occurs and the insoluble silver or thallium halide precipitates and can be removed by filtiation It is possible to use these techniques to transform compounds of Formula II into compounds of Formula III The removal of the coordinating ligands such as chloride or acetate is effected as described above in the presence of a neutral ligand L 1 e.g benzonitrile Removal of the coordinating ligand and addition of the neutral ligand is concomitant with addition of weakly or non-coordinating anions to give the compounds of Formula 111. With regards to the polymerisation reaction using the catalyst composition herein described, a feedstock comprising any source of carbon monoxide may be used Thus, the carbon monoxide may contain nitrogen, inert gases and up to 10% hydrogen Any olefin, can in theoiy, be used although the best reaction rates are obtained when either ethene oi a mixture of olefins, for example ethene propene and the like is used The lower rates obtained in the absence of ethene should not be construed as indicating that the piocess can only be used with an ethene feedstock since other olefins such as propene, 4,methylpentene- l , styrene, acrylates, vinyl acetates and the like all undeigo reaction to some extent A preferred polyketone is a terpolymei of ethene, piopene and carbon monoxide, under these circumstances the olefin will be a mixtuie of ethene and propene It is a feature of the piesent invention that wheie carbon monoxide is polymerised with a mixture of more than one olefin in particular ethylene and a second α-olefin foi a given ethylene/α-olefin ratio in the feedstock, polyketones prepared using the catalyst composition of the present invention have higher α- olefin contents than polyketones pi epared using pnoi art catalyst compositions This allows the α-olefin chaige to be i educed for a given α-oletin content in the final polymei The catalyst composition can be used in either the gas phase or the liquid phase It is to be understood that the term liquid phase also includes slurry phase where the polyketone product is insoluble in the reaction solvent Where the polymerisation is carried out in the gas phase, it is preferred to support the catalyst on a camei which can be for example polyketone polymer or an inorganic can lei foi example alumina oi silica Whei e the polymei isation process is carried out in the liquid phase, it is suitably carried out in a solvent which is chemically inert under the conditions employed and one in which the catalyst is soluble Moreover, the solvent like the anion should preferably be either weakly coordinating or non-coordinating Examples of such solvents include alcohols eg methanol, ethanol, propanol, ethers, glycol ethers and chlorinated solvents eg chloroform and dichloromethane Preferred solvents are methanol, ethoxyethanol, chloroform or dichloromethane, especially dichloromethane. Alternatively, an aliphatic tertiary alcohol can be used, preferably tertiary butanol. This can be used as a solvent on its own or in combination with an aprotic solvent eg ketones. A preferred solvent system is tertiary butanol/acetone mixture. It is also possible to use hydrocarbon solvents e.g. alkane (pentane, hexane, cyclohexane) or olefins especially where the olefin is a coreactant The solvent may contain small quantities of water for example up lo about 5% wt/wt The polymerisation process is suitably carried out at a temperature in the range of from 20 to 150°C, preferably 50 to 120°C and at elevated pressure, eg 1 to 100 bar. The overpressure of gas is suitably carbon monoxide or carbon monoxide and olefin, if the olefin is gaseous under the reaction conditions. The process may be operated batchwise continuously or in cascade The invention will be illustrated with reference to the following examples. Example 1 Et PN( n Bu)PEt 2 was prepared as follows PEt CI(0 589g, 4 7 mmol) was added dropwise to a Et O solution (20cm 3 ) of NH n Bu (0 ! 73g, 2 4 mmol) containing NEt ( I 4g) and stirred for one hour During this time a white precipitate was formed The supernatant containing the product was tillered and the solvent removed in vacuo yielding Et 2 PN( n Bu)PEt 2 as a clear liquid (0 499g, 2 0 mmol) :> ' P [ ' H] NMR (CD 2 CI 2 ) = 58.0 ppm Example 2 Ph 2 PN( n Bu)PPh was prepared as detailed in Example 1 with the following changes Ph 2 PCI ( 1.0g, 4 5 mmol) was added dropwise to a Et 2 0 solution (20cm 3 ) of NH 2 n Bιι (0 173g, 2 4 mmol) containing NEt 3 ( 1.4g) and stirred for 1 hour, yielding Ph 2 PN( n Bu)PPh 2 (0 848g, I 92 mmol) of product. 3 Jp fH] NMR (CD 2 CI 2 ) = 63.0 ppm Example 3 (PhO) 2 PN(Me) N( e)P(OPh) 2 was prepared following the general procedure as detailed in Chem. Ber 1994, 127, 1355 A mixture of corresponding alcohol (82.0mmol) and Et 3 N (84 Ommol) in n-hexane (50ml) was added dropwise to (CI 2 PN( e)N(lv1e)Pα ) (20 5mmol) also in n-hexane (200ml) at 25°C The reaction mixture was stirred for 2 hours and the Et NHCI was filtered off. Removal of the solvent in vacuo gave the analytically pure compound in 75-90% yield as a viscous liquid. Example 4 [Pd{Ph 2 PN(Me)N(Me)PPhj PhCN)j][BF 4 ] 2 was prepared as follows: Phenylmagnesium bromide (3m in Et 2 0)(9.563 gms, 30.6 mmol) was added dropwise to a solution of Cl 2 PN(Me)N(Me)PCI 2 (2.0 gms 7.6 mmol) in Et 2 0 (50 cm ) over a period of 30 mins. Stirring was continued for a further 30 mins, after which time the solids were allowed to settle. The supernatant was transferred to a second vessel containing [PdCODCI 2 ]( I gm, 3.5 mmol) in CH 2 CI 2 (50 cm 3 ) via filter cannula and the reaction monitored by P ninr When the addition was complete the solution was filtered through celite and the solvent removed in vacuo, affording [Pd{ Ph 2 PN(Me)N( e)PPh 2 |CI 2 ] as a yellow powder ( ! 9 gms 3.1 mmol). A solution of [Pd{ Ph 2 PN(Me)N(Me)PPh 2 }CI 2 ] (0.393 gms, 0.6 mmol) in CH 2 C1 2 (20 cm " ) was added dropwise to a suspension of AgBF 4 (0.379 gms, 1.9 mmol) in CH 2 CI 2 (20 cm '1 ) containing PhCN (0 6 is). A precipitate was immediately formed and stirrfng maintained for 30 mins After this time the solids were allowed to settle and the supernatant filtered through celite Removal of the solvent in vacua yielded [Pd { Ph 2 PN( e)N(Me)PPh 2 >(PhCN) 2 ][BF 4 ] 2 (0.41 lg, 0.4 mmol) as a yellow powder. ^'Pl 'H J NMR (CD 2 C1 2 ) = 1 7.5 ppm. Example 5 Ph PN(Et)P(Ph)N(Et)PPh was prepared as follows A solution of NH 2 E( (2m in THF) (50 cm 3 . 0. 1 mol) was added dropwise to a solution of PhPCh (3 Og, 1 .7 mmol) in Et 2 0 (50cm 3 at 0°C. Immediately a precipitate was formed and the mixtui e was stirred overnight The suspension was then filtered through celite, the supernatant collected and the solvent removed in vacuo. The resultant yellow oily residue was transferred to a vacuum distillation apparatus and distilled. A fraction, collected at ca 50°C, IO "2 mmHg was characterised as being the desired product, namely PPh(NHEt) 2 (0.64g, 3.3 mmol). A solution of PPh (NHEt) 2 (0.3 l g, 1 .5 mmol) in CH 2 CH 2 (20 cm 3 ) was added to PPh 2 CI (0.677g, 3.0 mmol) dissolved in CH 2 CI 2 (5 cm-') containing NEt 3 (0.466g, 4.6 mmol) and stirred \or two hours The solvent was removed in vacuo affording an off white solid. The solid was washed with 3 x 20 cm 3 aliquots of diethylether, the washings combined and the solvent then removed in vacuo yielding a white solid characterised as Ph 2 PN(Et)P(Ph)N(Et)PPh (0 540g, I 3 mmol) 3 1 P [H] NMR (CD 2 CI 2 ) = 53.5 [d, PPh 2 , 2I\ J (PP) 25] 105. 1 [t, PPh, J(PP) 25 Hz] ppm. Example 6 A copolymer of carbon monoxide and ethene was prepared as follows. CH CI 2 ( 1 10cm 3 ) was charged to a 300 cm 3 autoclave under nitrogen. The autoclave contents were pressurised to 30 bar G with a I : I mixture of carbon monoxide and ethene and heated to 70°C A solution of B(CβF5) (0. 16 lg, 0.310 mmol) in CH CI 2 ( 10 cm 3 ) was introduced followed by a procatalyst solution comprising Et 2 PN ( n Bu) PEt 2 (0 0039g, 0 01 mmol) prepared as detailed in Example I and palladium acetate (0 0035g, 0 01 mmol) in CH 2 C1 ( 10 cm 3 ) The pressure was adjusted to 50 bar G by the addition of a 1 I carbon monoxide/ethene mixture and this pressure maintained by the addition of the aforementioned gas mixture on demand After three hours, the pressure was released and the reaction was cooled to room temperature The polymer was collected by filtration and dried under reduced pressure 0 5g of copolymer was obtained. Example 7 The procedure of Example 6 was repeated using Ph 2 PN( n Bu) PPh 2 (0.0069g, 0.016 mmol) prepared as detailed in Example 2 and palladium acetate (0.0035g, 0.01 5 mmol) 6.823 of polymer was obtained Example 8 The procedure of Example 6 was repeated using a procatalyst solution of (PhO) 2 PN(Me)N(Me)P(OPh) 2 (0 O l Og, 0.020 mmol) prepared as detailed in Example 3 and palladium acetate (0.0045g, 0 020 mmol) A trace amount of polymer was obtained. Example 9 The procedure of Example 6 was repeated using a procatalyst solution of Ph 2 PN(Et)P(Ph)N(Et)PPh 2 (0 0089g, 0 016 mmol) prepared as detailed in Example 5 and palladium am me (0 0035g, 0 01 mmol) 4 070g of polymer was obtained. Example 10 Carbon monoxide/ethene co-polymer was prepared by substantially the same procedure to that detailed in Example 6, with the following differences' The procatalyst solution was comprised of [Pd{ Ph 2 PN(Me)N(Me)PPh 2 }(PhCN) 2 ][BF 4 ] 2 (O.O I 43g, O.O I όmmol), as prepared in Example 4 I 340g of polymer was obtained. Example 1 1 A carbon monoxide/ethene/propene ter-polymer was prepared by substantially the same procedure to that detailed in Example 6, with the following differences: The autoclave was initially charged with CH 2 CI 2 (90cm 3 ) and propene (24.58g 0.58mol). The procatalyst solution was comprised of Ph 2 PN( 'Bu)PPh (0.0069g, 0.015mmol), prepared in Example 2, and palladium acetate (0.0035g, O.O LSmmol). 1 .01 gms of polymer was obtained, containing 10.5 mole% of propylene. Example 12 Preparation of NMel P(G,H.,OMe-2)^ Addition of a solution of diisopropylamine [25 30g, 0.25mol] in ether [40ml] to a solution of phosphorus trichloride [ 10 90ml, l25mmol] in the same solvent [40ml] at - I 0°C resulted in the rapid formation of a white precipitate The mixture was stirred for two hours and then allowed to warm to room temperature Stirring was continued for a further hour and the mixture then filtered through celite to give an etheral solution containing the pioducl, CI>PN'Pι 2 1 Removal of the solvent /// vacuo afforded the product [20,262 , 0 2mol] as a pale yellow oil "Pl 'H] nmr (CF 2 CI 2 ) δp = I 70ppm BuLi [ 1 8 1 ml of a 2 2 1 M solution in hexanes, 4ιπmol] was added to a solution of anisole [432mg, 4mmol] in THF [5ml] and then stirred at room temperature for 2 hours The resulting solution of o-anisyl lithium was then added to a solution of 1 [404mg, 2mmol] in ether, and stirred at room temperature overnight to give a mixture containing the product, Ar 2 PN'Pr 2 as the only phosphorus containing species | P{ Η } nmr (CD 2 CI 2 ) δp = 21 ppm Anhydrous HCl [4ml of I M solution in ether, 4mιnol] was then added to the mixture obtained above immediately forming a white precipitate The resultant slurry was stirred at room temperature for 2 hours after which time the solvent was removed /// vacuo The residue was extracted with toluene and the slurry filtered through celite to yield a pale yellow solution containing the desired compound, Ar 2 PCI 2 Removal of the solvent in vacuo a H rded 2 as a pale yellow solid (505mgs, I Smmol) ' 'P j Η | nmr (CL ) .CL,.) δp = 7 1 ppm To a solution of 2 [500mg, 1 8mmol] in CH 2 CI 2 , NEt 3 [182mg, 1.8mmoI] was added followed by NMeH 2 [0 450ml of a 2M thf solution, 0 9mmol] The mixture was stirred for 30 mins and the solvent removed in vacuo The solid was extracted with toluene and the resultant slurry filtered through celite affording a colourless solution. The solvent was again removed /// vacuo to give NMe{P(Cr,H.ιOMe-2)2} 2 [420mg l .όmmol] as a white solid. Instead of extracting the solid using toluene it is possible instead to wash it using an alcohol, for example methanol, ethanol or isopropanol Example 13 A carbon monoxide/ethene/propene terpolymer was prepared as follows CH 2 CI 2 (SOCIT and propene ( 1 34g 0 32 mol) were charged to a 300cm' autoclave under nitrogen The autoclave contents were then pressurised to 25 bar G with a 1 I mixture of carbon monoxide and ethene and heated to 70°C A solution of B(C Λ F, (0 I 69g, 0 330mmol) in CH 2 CI 2 ( l Ocm') was introduced followed by a further lOcirf of CH 2 C Then the procatalyst solution comprising (C6H OMe-2)2PN(Me)P(C,,H.,OMe-2)2 (0 008, 0 O LSmmol), prepared as in Example 12, and palladium acetate (0 0035g, 0 015mmol) in CH 2 CI 2 ( 10cm J ) was added, followed by an additional 10cm ' of CH2CI2 The pressure was adjusted to 50 bar G by the addition of I I carbon monoxide/ethene and this pressure was maintained by the addition of the afoiementioned gas mixture on demand After 1 5 hours the gas uptake had visibly slowed and aftei 3 hours no further gas uptake was observed The polymei was collected by filtiation and dried under reduced pressure 1 5 30gms of polymer was obtained containing 5 3 mole% of propene n

Claims: Claims 1. A catalyst composition prepared by reacting together (a) a source of a Group Vll l metal (b) a bidentate phosphine ligand havmg at least two phosphorus atoms joined by a bridging group of the formula -(N) -(P) -N- where x is 0 or 1 and y is 0 oi I , and (c) a promoter. 2. A catalyst composition as claimed in Claim I wherein the bridging group is of the formula -( NRV(PRVNR 2 - where each R 2 is the same or different and R and R ' represent a monovalent organic group 3 A catalyst composition as claimed in either Claim 1 or Claim 2 wherein the bidentate ligand has the formula 1 R ' R 1 X P-(NRV(PRVNR 2 -P / 1 R' ' R' where each R 1 is independently an aryl. alkyl, alkoxy, amido or substituted derivative thereof R 2 is a hydrogen, a hydrocarbyl or hetero group, R ' is a hydrocarbyl or hetero group 4 A catalyst composition as claimed in any one of Claims I to 3 where x = y = 0 5. A catalyst composition as claimed in Claim 3 wherein at least one of the R 1 groups is an o-anisyl group 6 A catalyst composition as claimed in Claim 3 wherein x=y=0 and all R 1 groups are o-anisyl 7 A catalyst composition as claimed in any one of Claims I to 6 wherein the promoter is a source of either a non-coordinating or a weakly-coordinating anion. 8. A catalyst composition as claimed in any one of Claims I to 6 wherein the promoter is a boron hydrocarbyl compound. 9. A catalyst composition as claimed in Claim 8 wherein the boron hydrocarbyl compound is a compound of the formula BXYZ where at least one of X Y and Z is a monovalent hydrocarbyl group. 10. A catalyst composition as claimed in Claim 9 wherein the compound of formula BXYZ is B(C δ F s ) 3 . 11. A catalyst composition as claimed in Claim 9 wherein the compound of formula BXYZ is B(C f ,H 5 ).-.. 12. A catalyst composition as claimed in any one of Claims I to 6 wherein the promoter is an anion containing a plurality of boron atoms 13. A catalyst composition as claimed in any one of Claims I to 6 wherein the promoter is an aluminoxane. 14. A catalyst composition as claimed in any one of Claims I to 13 wherein the Group Vlll metal is palladium. 15. A process for preparing polyketones comprising contacting carbon monoxide and one or more ole ins in ihe presence of a catalyst composition as claimed in any one of Claims I to 14. 16. A process for preparing polyketones as claimed in Claim I 5 wherein carbon monoxide is contacted with ethylene and propylene 17. A compound of the formula (o-anisyl) 2 PX where X is Cl, Br or F. 18. A compound as claimed in Claim 17 wherein X is Cl. 19. A method for preparing (o-anisyl) 2 PCI comprising in a first step reacting o-anisyl with R 2 NPC1 2 where R is a hydrocarbyl group and in a second step treating the product of the first step with a Bronsted acid. 20. A compound of the formula (r<'),p-(N) -(P) -N-P(R')2 where x and y are independently I or U and R 1 is as defined in Claim 3 and at least one of the R 1 groups is an o-anisyl. 21 . A compound as claimed in Claim 20, having the formula ( K l ) PNR 2 P(R 1 ), where R is a hydrogen, a hydrocarbyl or hetero group 22. A compound as claimed in Claim 21 having the formula (Ph) 2 PN(nBtι)P(Q-anisyl) 2 23. A compound as claimed in Claim 21 wherein all R 1 groups are o-anisyl. 24. A compound as claimed in Claim 23 wherein R 2 is methyl. 25. A process for preparing a compound as claimed in Claim 23 comprising reacting (o-anisyl) 2 PX where X is Cl, Br or F with NH 2 R 2 where R 2 is as defined in Claim 21 in the presence of a base. 26. A compound of formula 11 where each L is independently a monodentate ligand or L 2 taken together is a bidentate ligand, P-P is a bidentate phosphine ligand having at least two phosphorus atoms joined by a bridging group of the formula -(N) -(P) V -(N)- where x and y are independently I or 0, provided that when x=0 and y=0 L is not Cl and when L is Cl and P-P is (R 7 ) 2 PN(Me)N(Me)P(R 7 ) 2 , R 7 is not alkoxy 27. A compound of the formula HI [L' 2 Pd(P-P)](A) 2 III where P-P is as defined in Claim 26, L 1 is a neutral monodentate ligand or L' 2 taken together is a neutral bidentate ligand and A is a weakly or non-coordinating anion or (A) 2 together is a weakly or non-coordinating dianion i o

Inventors: DOSSETT STEPHEN JOHN, DOSSETT, STEPHEN, JOHN
Applicants: BP CHEM INT LTD, DOSSETT STEPHEN JOHN, BP CHEMICALS LIMITED, DOSSETT, STEPHEN, JOHN
Application year: 1997
Main classification: B01J31
IPC codes: B01J31, C07F9, C08G67