WO2020200681A1

WO2020200681A1 - Polymerization method

Info

Publication number: WO2020200681A1
Application number: PCT/EP2020/056572
Authority: WO
Inventors: Franziska SCHÖNEBECK; Guillaume MAGNIN; Jamie CLIFTON
Original assignee: Rheinisch-Westfälische Technische Hochschule (Rwth) Aachen
Priority date: 2019-04-02
Filing date: 2020-03-11
Publication date: 2020-10-08

Abstract

The present invention relates to polymerization method of aromatic, hetero aromatic, alkenyl and alkinyl monomers with a Pd(I)-catalyst.

Description

Polymerization method

D e s c r i p t i o n

The present invention relates to the field of the polymerization of organic molecules, especially aromatic molecules, alkene and alkynes

Organic polymers, especially polymers whose chain consists entirely or predominantly of conjugated carbons, are of ever-increasing importance in many areas, e.g. areas such as organic electronics, solar cells or fuel cell developments.

Therefore there is a constant need for polymerization methods for organic molecules, especially polymeric organic molecules whose chain is made up of aromatic, alkenyl or alkinyl molecules, and therefore it is an object for the skilled person to provide such methods.

This object is met by the method of Claim 1 of the present invention. Accordingly, a polymerization method is provided, including a chain-prolongating step of forming a carbon- carbon-bond between a sp² or sp-hybridized carbon with an at least formally nucleophilic leaving group and a sp² or sp-hybridized carbon with an at least formally electrophilic leaving group in the presence of a Pd(I)-compound. Surprisingly, it has been found that by doing so for a broad variety of suitable monomers a polymerization occurs. For most applications within the present invention, at least one of the following advantages could be observed:

The reaction usually proceeds smoothly and straightforwardly

The reaction proceeds extremely rapidly, often being finished within seconds to one or several minutes

The reaction can be used with a broad range of monomers

The reaction can be performed at room temperature or slightly elevated or lower temperatures

Many of the Pd(I) catalysts that are suitable within the present invention are air-stable The polymerization can also be performed in the presence of oxygen/air.

The terms of the inventive method are explained in the following whereby all preferred embodiments may be combined ad libitum :

The term“chain-prolongating step” especially includes and/or means that the polymeric chain of the polymer is synthesized by involvement of the method of the present invention. It goes without saying that other polymerization reactions may be involved as well, e.g. when (block) copolymers are synthesized. The term“chain-prolongating” does not exclude that the inventive method is used for side chains (e.g. when branched polymers are synthesized) or to modify the polymer without lengthening it.

The term“sp² or sp-hybridized” especially means that the carbon atoms inbetween the bond is formed are part of a (hetero)aromatic, alkenyl or alkinyl moiety.

In other words, according to a preferred embodiment of the present invention, the

polymerization method comprises the polymerization of aromatic, heteroaromatic, alkenyl or alkinyl molecules. It should be noted that according to the present invention the hybridization state of the two bond forming carbons is not changed.

The term“sp² or sp-hybridized carbon with an at least formally nucleophilic leaving group” especially means that before the carbon-carbon bond formation occurs there is a group bound to the carbon which can act as nucleophile after leaving the carbon. It should be noted that in the course of the inventive procedure this may or may not be the case as - without being bound to any theory - the inventors believe that the actual reaction mechanism may be very complex.

The term“nucleophilic” especially means and/or includes that the group (after it is no longer bound to the carbon) contains a free electron pair and is thus a Lewis-base.

Preferred nucleophile leaving groups include halogens, pseudohalogens, organic and inorganic ethers and esters, with triflates, tosylates, mesylates especially preferred. Most preferred nucleophilic leaving groups are bromides.

The term“sp² or sp-hybridized carbon with a formal electrophilic leaving group” especially means that before the carbon-carbon bond formation occurs there is a group bound to the carbon which can act as electrophile after leaving the carbon. Again, it should be noted that in the course of the inventive procedure this may or may not be the case as - without being bound to any theory - the inventors believe that the actual reaction mechanism may be very complex.

The term“electrophilic” especially means and/or includes that the group (after is no longer bound to the carbon) contains or forms a Lewis-acid. Preferred electrophilic leaving groups include metals or - when the metal has an at least formal oxidation state of greater than (I) - metal compounds of the structure MR_X with M being the metal, R being an at least formally nucleophilic leaving group as defined above and x being 1 or greater but smaller than the (formal) oxidation state of the metal M. Preferred metals include alkaline metals, earth alkaline metals and zinc, with lithium, magnesium and zinc being especially preferred.

It should be noted that the formal electrophilic leaving group will in many applications be formed either in substance or in situ by suitable metallation reactions

The term“in the presence of’ is to be understood in its broadest form and may include the intermediate coordination or bond formation of one or both of the carbons to a palladium atom.

The term“Pd(I)-compound” especially includes a chemical compound which contains palladium in the formal oxidation state (I). The present method is, however, not limited to applications or embodiments where the Pd(I)-compound is present at the beginning, according to embodiments of the present invention the Pd(I)-compound may also be formed in situ. The Pd(I) -compound may be present in solvated form or on a solid carrier, or to put it otherwise the reaction maybe homogenous or heterogeneous.

According to an embodiment of the present invention, as previously described, the Pd(I)- compound is formed in situ during the reaction from one or more suitable precursor compound(s).

Suitable methods or reaction steps to form the Pd(I)-compound, either in situ or synthetically include:

1) Oxidation of Pd(0) to Pd(I) The Pd(I)-compound can be formed from Pd(0)-precursors using suitable oxidants. Reagents found useful include aryl halide or aryl pseudohalide compounds, because it has been found that those compounds often react smoothly with the halogen or pseudohalogen compound becoming a ligand.

Alternatively the Pd(I)-compound can be formed using a SET (single electron transfer) process using suitable oxidants or even electrolysis. Suitable oxidants are oxygen or certain salts such as CuBr, CuBr2, AgBr, AuBr3, FeBr3; some suitable methods are inter alia described in Angew. Chem. Int. Ed. 2012, 51, 7226 and Angew. Chem. Int. Ed. 2017, 56,1581

Similarly, Pd(0)(PtBu₃)₂ can be oxidized to Pd(I) in the presence of oxygen/air, a halide salt (e.g. NMe4l) and an organometallic reagent (such as RMgX or RZnX). See: Angew. Chem.

Int. Ed. 2017, 56,1581

Especially preferred Pd(0)-compounds include Pd(0)-complexes, especially Pd2(dba)3 or Pd(0)(PtBu₃)2

2) Comproportionation of Pd

Using suitable Pd(0) and Pd(II) precursors, the Pd(I) -compound can be formed via a comproportionation reaction. Suitable Pd(0)-compounds include Pd(0)-complexes, especially Pd(PtBu3)2_. Suitable Pd(II)-compounds include Pdl ₂ .

3) Reduction of Pd(II)-compounds

The Pd(I)-compound can be formed from Pd(II) -precursors using suitable reductants or e.g. PtBu3 directly. Suitable methods are inter alia disclosed in J. Am. Chem. Soc. 2017, 139, 5194 According to a preferred embodiment of the present invention, the Pd(I)-compound comprises an electron-donating ligand. Especially preferred ligands are phosphines and carbenes, with phosphines especially preferred.

These Pd(I)-compounds either can be prepared as a compound or can be generated in situ using the methods shown above or via ligand-exchange reactions from other Pd(I)-precursors.

According to a preferred embodiment of the present invention the Pd(I)-compound comprises a phosphine ligand of the form PR¹R²R³ with R¹ to R³ independently selected out of the group comprising alkyl, cycloalkyl, halogenalkyl, aryl, halogenaryl, heteroaryl.

According to a preferred embodiment of the present invention, the Pd(I)-compound comprises a carbene ligand selected from the following structures I to IV:

Structure I)

whereby R¹ to R³ are independently selected out of a group comprising alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, hetero arylene, heterocycloalkylene, heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, formyl, carboxy- and/or carbonyl derivatives, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether, silylalkyl, silylalkyloxy, whereby at suitable residues one or more Cth-groups may independently from each other substituted by -O-, -S-, -NH-, -NR°-, - SiR°R°°-, -CO-, -COO-, -OCO-, -OCO-O-, -SO2-, -S-CO-, -CO-S-, -CY1=CY2 or -CºC- in that way that O and/or S atoms are not directly bound to each other; terminal CH₃ groups are understood as CH₂-H groups

R⁴ to R⁷ are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene, heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether, silylalkyl, silylalkyloxy, whereby at suitable residues one or more CH₂-groups may independently from each other substituted by -O-, -S-, -NH-, -NR°-, - SiR°R°°-, -CO-, -COO-, -OCO-, -OCO-O-, -SO2-, -S- CO-, -CO-S-, -CY 1=CY2 or -CºC- in that way that O and/or S atoms are not directly bound to each other; terminal CH₃ groups are understood as CH₂-H groups

And whereby R¹ to R⁷ may be so substituted that a ring is formed between R² and R³, R⁴ and R³, R⁶ and R⁷, R¹ and R⁴/R⁵, R⁴/R⁵ and R⁶/R⁷or R²/R³ and R⁶/R⁷

Structure II)

whereby R¹ to R³ are independently selected out of a group comprising alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, hetero arylene, heterocycloalkylene, heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, formyl, carboxy- and/or carbonyl derivatives, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether, silylalkyl, silylalkyloxy, whereby at suitable residues one or more CH₂-groups may independently from each other substituted by -O-, -S-, -NH-, -NR°-, - SiR°R°°-, -CO-, -COO-, -OCO-, -OCO-O-, -SO2-, -S-CO-, -CO-S-, -CY1=CY2- or -CºC- in that way that O and/or S atoms are not directly bound to each other; terminal CH₃ groups are understood as CH₂-H groups

R⁴ to R⁷ are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene, heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether, silylalkyl, silylalkyloxy, whereby at suitable residues one or more CH₂-groups may independently from each other substituted by -O-, -S-, -NH-, -NR°-, -SiR°R°°-, -CO-, -COO-, -OCO-, -OCO-O-, -SO2-, -S- CO-, -CO-S-, -CY 1=CY2 - or -CºC- in that way that O and/or S atoms are not directly bound to each other; terminal CH₃ groups are understood as CH₂-H groups and whereby R¹ to R⁷ may be so substituted that a ring is formed between R² and R³, R¹ and R²/R³ or R²/R³ and R⁷ or R⁶ and R⁷ or R⁵ and R⁶ or R⁴ and R⁵

Structure III)

whereby R¹ and R² may either be substituted or unsubstituted carbon or nitrogen, with the proviso that not R¹ and R² are both nitrogen, and whereby the substitution may be selected from hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene, heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl,

halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether, silylalkyl, silylalkyloxy, whereby at suitable residues one or more CH₂-groups may independently from each other substituted by -O-, -S-, -NH-, -NR°-, - SiR°R°°-, -CO-, -COO-, -OCO-, -OCO-O-, -SO2-, -S-CO-, -CO-S-, -CY1=CY2- or -CºC- in that way that O and/or S atoms are not directly bound to each other; terminal CH₃ groups are understood as CH₂-H groups

R² and R⁴ are independently selected out of a group comprising alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene, heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, formyl, carboxy- and/or carbonyl derivatives, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether, silylalkyl, silylalkyloxy, whereby at suitable residues one or more CH₂-groups may independently from each other substituted by -O-, -S-, -NH-, -NR°-, - SiR°R°°-, -CO-, -COO-, -OCO-, -OCO-O-, -SO2-, -S-CO-, -CO-S-, -CY1=CY2- or -CºC- in that way that O and/or S atoms are not directly bound to each other; terminal CH₃ groups are understood as CH₂-H groups, whereby the bond between R¹ and R² may be a single or a double bond, and whereby R¹ to R⁴ may be so substituted that a ring is formed between R¹ and R², R¹ and R³, R¹ and R⁴, R² and R³ or R² and R⁴ _.

IV)

whereby R³ und R⁴ are defined as in Structure III and Xi and X2 may independent from each other be O, S, CH2 and NH. Generic group definition: Throughout the description and claims generic groups have been used, for example alkyl, alkoxy, aryl. Unless otherwise specified the following are preferred groups that may be applied to generic groups found within compounds disclosed herein: alkyl: linear and branched C1-C8-alkyl, long-chain alkyl: linear and branched C5-C20 alkyl alkenyl: C2-C6-alkenyl, cycloalkyl: C3-C8-cycloalkyl, alkoxy: C1-C6-alkoxy, long-chain alkoxy: linear and branched C5-C20 alkoxy alkylene: selected from the group consisting of:

methylene; 1,1-ethylene; 1,2-ethylene; 1,1-propylidene; 1,2-propylene; 1,3- propylene; 2,2- propylidene; butan-2-ol-l,4-diyl; propan-2-ol-l,3-diyl; 1, 4-butylene; cyclohexane- 1,1-diyl; cyclohexan-l,2-diyl; cyclohexan-1,3- diyl; cyclohexan-l,4-diyl; cyclopentane- 1,1-diyl;

cyclopentan-l,2-diyl; and cyclopentan-l,3-diyl, aryl: selected from homoaromatic compounds having a molecular weight under 300, arylene: selected from the group consisting of: 1,2-phenylene; 1,3- phenylene; 1,4-phenylene;

1.2-naphtalenylene; 1,3-naphtalenylene; 1,4- naphtalenylene; 2,3-naphtalenylene; 1-hydroxy-

2.3-phenylene; 1 -hydroxy-2,4- phenylene; 1 -hydroxy-2,5- phenylene; and 1 -hydroxy-2, 6- phenylene, heteroaryl: selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; thiophenyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl, heteroarylene: selected from the group consisting of: pyridindiyl; quinolindiyl; pyrazodiyl; pyrazoldiyl; triazolediyl; thiopheninyl; pyrazindiyl; and imidazolediyl, wherein the heteroarylene acts as a bridge in the compound via any atom in the ring of the selected heteroarylene, more specifically preferred are: pyridin-2, 3-diyl; pyridin-2,4-diyl; pyridin-2, 5- diyl; pyridin-2, 6-diyl; pyridin-3,4- diyl; pyridin-3,5-diyl; quinolin-2, 3-diyl; quinolin-2,4-diyl; quinolin-2, 8-diyl; isoquinolin-1, 3-diyl; isoquinolin-l,4-diyl; pyrazol-1, 3-diyl; pyrazol-3,5- diyl; triazole-3, 5-diyl; triazole- 1, 3-diyl; pyrazin-2,5-diyl; and imidazole-2, 4-diyl, a -C1-C6- heterocycloalkyl, wherein the heterocycloalkyl of the -Cl -C6-heterocycloalkyl is, selected from the group consisting of: piperidinyl; piperidine; 1,4-piperazine, tetrahydro thiophene; tetrahydrofuran; 1,4,7-triazacyclononane; 1,4,8,11- tetraazacyclotetradecane; 1,4,7,10,13- pentaazacyclopentadecane; 1,4-diaza- 7-thia-cyclononane; 1,4- diaza-7-oxa-cyclononane; 1,4,7, 10-tetraazacyclododecane; 1,4-dioxane; 1,4, 7-trithia-cyclononane; pyrrolidine; and tetrahydropyran, wherein the heterocycloalkyl may be connected to the -C1-C6-alkyl via any atom in the ring of the selected heterocycloalkyl, heterocycloalky lene: selected from the group consisting of: piperidin-1,2- ylene; piperidin- 2,6-ylene; piperidin-4,4-ylidene; l,4-piperazin-l,4-ylene; l,4-piperazin-2,3-ylene; 1,4- piperazin-2,5-ylene; l,4-piperazin-2,6-ylene; 1,4-piperazin- 1,2-ylene; 1,4-piperazin- 1,3- ylene; 1,4-piperazin- 1,4-ylene; tetrahydrothiophen-2,5-ylene; tetrahydrothiophen-3,4-ylene; tetrahydrothiophen-2,3-ylene; tetrahydrofuran-2,5-ylene; tetrahydrofuran- 3,4-ylene;

tetrahydrofuran-2,3-ylene; pyrrolidin-2,5-ylene; pyrrolidin-3,4-ylene; pyrrolidin-2,3-ylene; pyrrolidin- 1,2-ylene; pyrrolidin- 1,3 -ylene; pyrrolidin-2,2-ylidene; l,4,7-triazacyclonon-l,4- ylene; 1,4,7- triazacyclonon-2,3-ylene; l,4,7-triazacyclonon-2,9-ylene; 1,4,7-triazacyclonon- 3,8-ylene; l,4,7-triazacyclonon-2,2- ylidene; l,4,8,l l-tetraazacyclotetradec-l,4-ylene;

1,4,8,11- tetraazacyclotetradec- 1,8 -ylene; 1,4,8, l l-tetraazacyclotetradec-2,3-ylene; 1,4,8,11- tetraazacyclotetradec-2,5-ylene; 1,4,8,11- tetraazacyclotetradec- 1,2-ylene; 1,4,8,11- tetraazacyclotetradec-2,2-ylidene; 1,4,7, 10-tetraazacyclododec-l,4-ylene; 1,4,7,10- tetraazacyclododec-l,7-ylene; l,4,7,10-tetraazacyclododec-l,2- ylene; 1,4,7,10- tetraazacyclododec-2,3- ylene; 1,4,7, 10-tetraazacyclododec-2,2-ylidene; 1,4,7,10,13 pentaazacyclopentadec-l,4-ylene; 1,4,7,10,13- pentaazacyclopentadec-l,7-ylene; 1,4,7,10,13- pentaazacyclopentadec-2,3- ylene; l,4,7,10,13-pentaazacyclopentadec-l,2-ylene; 1,4,7,10, 13-pentaazacyclopentadec-2,2-ylidene; l,4-diaza-7-thia-cyclonon- 1,4-ylene; l,4-diaza-7- thia-cyclonon- 1,2-ylene; l,4-diaza-7thia-cyclonon- 2,3-ylene; l,4-diaza-7-thia-cyclonon-6,8- ylene; l,4-diaza-7-thia-cyclonon- 2,2-ylidene; l,4-diaza-7-oxacyclonon- 1,4-ylene; 1,4-diaza-

7-oxa-cyclonon- 1,2-ylene; l,4diaza-7-oxa-cyclonon-2,3-ylene; l,4-diaza-7-oxa-cyclonon-6,

8-ylene; l,4-diaza-7-oxa-cyclonon-2,2-ylidene; l,4-dioxan-2,3-ylene; 1,4- dioxan-2,6-ylene;

1 ,4-dioxan-2,2-ylidene; tetrahydropyran-2,3-ylene; tetrahydropyran-2,6-ylene;

tetrahydropyran-2,5-ylene; tetrahydropyran-2,2- ylidene; l,4,7-trithia-cyclonon-2,3-ylene; l,4,7-trithia-cyclonon-2,9- ylene; and l,4,7-trithia-cyclonon-2,2-ylidene, heterocycloalkyl: selected from the group consisting of: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1,4-piperazinyl; tetrahydrothiophenyl;

tetrahydrofuranyl; 1,4,7- triazacyclononanyl; 1,4,8, 11 -tetraazacyclotetradecanyl; 1,4,7,10,13- pentaazacyclopentadecanyl; l,4-diaza-7-thiacyclononanyl; l,4-diaza-7-oxa- cyclononanyl; 1,4,7, 10-tetraazacyclododecanyl; 1,4-dioxanyl; 1,4,7- trithiacyclononanyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl, amine: the group -N(R)2 wherein each R is independently selected from: hydrogen; C1-C6- alkyl; C1-C6-alkyl-C6H5; and phenyl, wherein when both R are C1-C6-alkyl both R together may form an - NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring, halogen/halide: selected from the group consisting of: F; C1; Br and I, halogenalkyl: selected from the group consisting of mono, di, tri-, poly and perhalogenated linear and branched C1-C8-alkyl pseudohalogen/pseudohalide: selected from the group consisting of -CN, -SCN, -OCN, N3, - CNO, -SeCN sulphonate: the group -S(0)20R, wherein R is selected from: hydrogen; C1-C6-alkyl; phenyl; C1-C6-alkyl-C6H5 ; Li; Na; K; Cs; Mg; and Ca, sulphate: the group -0S(0)20R, wherein R is selected from: hydrogen; C1-C6-alkyl; phenyl; C1-C6-alkyl-C6H5 ; Li; Na; K; Cs; Mg; and Ca, sulphone: the group -S(0)2R, wherein R is selected from: hydrogen; C1-C6- alkyl; phenyl; C1-C6-alkyl-C6H5 and amine (to give sulphonamide) selected from the group: -NR'2, wherein each R’ is independently selected from: hydrogen; C1-C6-alkyl; ClC6-alkyl-C6H5; and phenyl, wherein when both R' are C1-C6-alkyl both R’ together may form an -NC3 to an -NCS heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring, carboxylate derivative: the group -C(0)OR, wherein R is selected from: hydrogen; C1-C6- alkyl; phenyl; C1-C6-alkyl-C6H5; Li; Na; K; Cs; Mg; and Ca, carbonyl derivative: the group -C(0)R, wherein R is selected from: hydrogen; C1-C6-alkyl; phenyl; C1-C6-alkyl-C6H5 and amine (to give amide) selected from the group: -NR'2, wherein each R’ is independently selected from: hydrogen; C1-C6-alkyl; C1-C6-alkyl-C6H5; and phenyl, wherein when both R’ are C1-C6- alkyl both R' together may form an -NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring, phosphonate: the group -P(O) (OR) 2, wherein each R is independently selected from:

hydrogen; C1-C6-alkyl; phenyl; C1-C6-alkyl-C6H5; Li; Na; K; Cs; Mg; and Ca, phosphate: the group -OP(0)(OR)2, wherein each R is independently selected from:

hydrogen; C1-C6-alkyl; phenyl; C1-C6-alkyl-C6H5; Li; Na; K; Cs; Mg; and Ca, phosphine: the group -P(R)2, wherein each R is independently selected from: hydrogen; C1- C6-alkyl; phenyl; and C1-C6-alkyl-C6H5, phosphine oxide: the group -P (O) R2, wherein R is independently selected from: hydrogen; C1-C6-alkyl; phenyl; and C1-C6-alkyl-C6H5; and amine (to give phosphonamidate) selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen; C1-C6- alkyl; C1-C6-alkyl-C6H5; and phenyl, wherein when both R' are C1-C6-alkyl both R' together may form an -NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring. polyether: chosen from the group comprising-(O-CH₂-CH(R))_n-OH and -(O-CH₂-CH(R))_n-H whereby R is independently selected from: hydrogen, alkyl, aryl, halogen and n is from 1 to 250 silylalkyl: the group - S1R3, whereby each R is independently selected from: hydrogen; Cl- C6-alkyl; C1-C6-alkyl-C6H5; and phenyl, wherein when both R are C1-C6-alkyl both R together may form an - NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring Silylalkyloxy: the group - OS1R3, whereby each R is independently selected from: hydrogen; C1-C6-alkyl; C1-C6-alkyl-C6H5; and phenyl, wherein when both R are C1-C6-alkyl both R together may form an - NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring.

Unless otherwise specified the following are more preferred group restrictions that may be applied to groups found within compounds disclosed herein: alkyl: linear and branched C1-C6-alkyl, more preferred methyl, ethyl, propyl, isopropyl, buyl, isobutyl long-chain alkyl: linear and branched C5-C10 alkyl, preferably linear C6-C8 alkyl alkenyl: C3-C6-alkenyl, cycloalkyl: C6-C8-cycloalkyl, alkoxy: C1-C4-alkoxy, long-chain alkoxy: linear and branched C5-C10 alkoxy, preferably linear C6-C8 alkoxy alkylene: selected from the group consisting of: methylene; 1,2-ethylene; 1,3-propylene; butan-2-ol-l,4-diyl; 1,4-butylene; cyclohexane- 1,1-diyl; cyclohexan-l,2-diyl; cyclohexan-1,4- diyl; cyclopentane- 1,1-diyl; and cyclopentan-l,2-diyl, aryl: selected from group consisting of: phenyl; biphenyl; naphthalenyl; anthracenyl; and phenanthrenyl, arylene: selected from the group consisting of: 1,2-phenylene; 1,3- phenylene; 1,4-phenylene; 1,2-naphtalenylene; 1,4-naphtalenylene; 2,3- naphtalenylene and 1 -hydroxy-2, 6-phenylene, heteroaryl: selected from the group consisting of:

pyridinyl; pyrimidinyl; quinolinyl; pyrazolyl; thiophenyl; triazolyl; isoquinolinyl; imidazolyl; and oxazolidinyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl, heteroarylene: selected from the group consisting of:

pyridin 2,3-diyl; pyridin-2,4-diyl; pyridin-2,6-diyl; pyridin-3,5-diyl; quinolin-2,3-diyl;

quinolin-2,4-diyl; isoquinolin-l,3-diyl; isoquinolin-l,4-diyl; pyrazol-3,5-diyl; and imidazole- 2, 4-diyl, heterocycloalkyl: selected from the group consisting of:

pyrrolidinyl; morpholinyl; piperidinyl; thiopheninyl; piperidinyl; 1,4 piperazinyl;

tetrahydrofuranyl; 1,4,7-triazacyclononanyl; 1,4,8, 11-tetraazacyclotetradecanyl; 1,4,7,10,13- pentaazacyclopentadecanyl; 1,4,7,10-tetraazacyclododecanyl; and piperazinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl, heterocycloalkylene: selected from the group consisting of:

piperidin-2,6-ylene; piperidin-4,4-ylidene; l,4-piperazin-l,4-ylene; l,4-piperazin-2,3-ylene; l,4-piperazin-2,6-ylene; tetrahydrothiophen-2,5-ylene; tetrahydrothiophen-3,4-ylene;

tetrahydrofuran-2,5-ylene; tetrahydrofuran-3,4-ylene; pyrrolidin-2,5-ylene; pyrrolidin-2,2- ylidene; l,4,7-triazacyclonon-l,4- ylene; l,4,7-triazacyclonon-2,3-ylene; 1,4,7- triazacyclonon-2,2-ylidene; 1,4,8,11- tetraazacyclotetradec-l,4-ylene; 1,4,8,11- tetraazacyclotetradec-l,8-ylene; 1,4,8, 1 l-tetraazacyclotetradec-2,3-ylene; 1,4,8, 11- tetraazacyclotetradec-2,2-ylidene; 1,4,7, 10-tetraazacyclododec-l,4-ylene; 1,4,7,10- tetraazacyclododec- 1 ,7 -ylene; 1 ,4,7, 10-tetraazacyclododec-2,3-ylene; 1 ,4,7 , 10- tetraazacyclododec-2,2-ylidene; 1,4,7,10,13- pentaazacyclopentadec-l,4-ylene; 1,4,7,10,13- pentaazacyclopentadec-l,7-ylene; l,4-diaza-7-thia-cyclonon-l,4 ylene; l,4-diaza-7-thia- cyclonon-2,3-ylene; l,4-diaza-7-thia cyclonon-2,2-ylidene; l,4-diaza-7-oxa-cyclonon-l,4- ylene; 1,4 diaza-7-oxa-cyclonon-2,3-ylene;l,4-diaza-7-oxa-cyclonon-2,2- ylidene; 1,4- dioxan-2,6-ylene; l,4-dioxan-2,2-ylidene; tetrahydropyran-2,6-ylene; tetrahydropyran-2,5- ylene; and tetrahydropyran- 2,2-ylidene, a -C1-C6-alkyl-heterocycloalky, wherein the heterocycloalkyl of the -C1-C6-heterocycloalkyl is selected from the group consisting of: piperidinyl; 1,4-piperazinyl; tetrahydrofuranyl; 1,4,7- triazacyclononanyl; 1,4,8,11- tetraazacyclotetradecanyl; 1,4,7,10,13- pentaazacyclopentadecanyl; 1,4,7,10- tetraazacyclododecanyl; and pyrrolidinyl, wherein the heterocycloalkyl may be connected to the -C1-C6- alkyl via any atom in the ring of the selected heterocycloalkyl, amine: the group -N (R) 2, wherein each R is independently selected from: hydrogen; C1-C6- alkyl; and benzyl, halogen: selected from the group consisting of: F and Cl, sulphonate: the group -S(0)20R, wherein R is selected from: hydrogen; C1-C6-alkyl; Na; K; Mg; and Ca, sulphate: the group -0S(0)20R, wherein R is selected from: hydrogen; C1-C6-alkyl; Na; K; Mg; and Ca, sulphone: the group -S(0)2R, wherein R is selected from: hydrogen; C1-C6- alkyl; benzyl and amine selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen; C1-C6-alkyl; and benzyl, carboxylate derivative: the group -C(0)OR, wherein R is selected from hydrogen; Na; K; Mg; Ca; C1-C6-alkyl; and benzyl, carbonyl derivative: the group: -C(0)R, wherein R is selected from: hydrogen; C1-C6-alkyl; benzyl and amine selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen; C1-C6-alkyl; and benzyl, phosphonate: the group -P(O) (OR)2, wherein each R is independently selected from:

hydrogen; C1-C6-alkyl; benzyl; Na; K; Mg; and Ca, phosphate: the group -OP(O) (OR)2, wherein each R is independently selected from:

hydrogen; C1-C6-alkyl; benzyl; Na; K; Mg; and Ca, phosphine: the group -P(R)2, wherein each R is independently selected from: hydrogen; C1- C6-alkyl; and benzyl, phosphine oxide: the group -P(0)R2, wherein R is independently selected from: hydrogen; C1-C6-alkyl; benzyl and amine selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen; C1-C6-alkyl; and benzyl. polyether: chosen from the group comprising-(O-CH₂-CH(R))_n-OH and -(O-CH₂-CH(R))_n-H whereby R is independently selected from: hydrogen, methyl, halogen and n is from 5 to 50, preferably 10 to 25.

M, Mn (n being an integer): Metals (either charged or uncharged), whereby two Metals Mn and Mm are independently selected from each other unless otherwise indicated.

According to a preferred embodiment the Pd(I)-compound may be monomeric, whereby the term“monomeric” is to be understood that the compound comprises only one palladium atom.

However, according to an alternative and also preferred embodiment the Pd(I)-compound may be dimeric, whereby the term“dimeric” is to be understood that the compound comprises two palladium atoms. If the Pd(I)-compound is dimeric then it is especially preferred that the Pd(I)-compound comprises a compound where there is a bond between the two palladium atoms. Especially preferred are compounds of the following structure:

With R¹ and R² being independent from each other electron donating ligands, especially phosphines and/or carbenes, most preferred phosphines and R³ and R⁴ independently from each other halogen, with iodide being preferred, or pseudohalogen. Preferably at least one of R³ and R⁴ are iodide.

According to a preferred embodiment of the present invention R³ and/or R⁴ are iodide, preferably both are iodide and R¹ = R².

When R³ and/or R⁴ are iodide and R¹ = R² then many of the compounds can easily be synthesized from the monomeric Pd-compounds, which are depending on the compound e.g. synthesizable as described in Org. Lett., 2018, 20 (18), pp 5537-5540 or analogous methods, by reaction with iodine.

Especially preferred are compounds in which R¹ and R² as well as R³ and R⁴ are identical. Amongst these compounds, compounds are preferred where R¹ and R² is phosphine and R³ and R⁴ is halogen, especially iodide. Many of these compounds can be formed in situ from suitable Pd(II) and Pd(0)precursors.

Suitable monomers that are able to be polymerized using the inventive method comprise (hetero)aromatic, alkenic and alkinic molecules. Aromatic molecules may include molecules with one aromatic ring, such as a benzene or heteroaromatic ring. Alternatively several aromatic rings, including fused rings and may be present, whereby any of the rings can be aromatic or heteroaromatic.

Depending on the polymer that is intended to obtain, one or more of the following synthesis strategies can be used:

I)

One possible synthesis strategy is to use a monomer which initially comprises two sp² or sp- hybridized carbons with an at least formally nucleophilic leaving group , whereby as a first step approximately half of those nucleophilic leaving groups are converted to electrophilic leaving groups by suitable methods. In case that the electrophilic leaving group is a metal or metal compound then metallization methods and transmetalation reactions can be used, e.g. (but not limited to):

Reaction with organomagnesium or a magnesium compound, alternatively with lithium or a organolithium compound, then - depending on the application- transmetalation with e.g. a zinc salt to form a organozinc compound

The so-contained monomer is then subjected to the polymerization using a Pd(I)-compound.

II)

Alternatively it can be advantageous to use two different monomers, i.e. one monomer which contains two sp² or sp-hybridized carbons with an at least formally nucleophilic leaving group (whereby the nucleophilic leaving groups can be identical or different) and a different monomer which contains two sp² or sp-hybridized carbons with an at least formally electrophilic leaving group (whereby again the electrophilic leaving groups can be identical or different).

It goes without saying that - depending on the synthesis strategy - the monomer which contains two sp² or sp-hybridized carbons with an at least formally electrophilic leaving group can be synthesized via metalation or transmetalation reactions as described above.

The inventive method is preferably carried out in a an aprotic solvent, with ethers, especially cyclic ethers and aromatic compounds, such as toulene or benzene being preferred.

The content of the Pd(I)-compound (in mol% based on the total monomer concentration prior to the reaction) is preferably ³ 0.05 % to £ 1%. Preferred concentration which have been shown to be advantageous for most reactions are ³ 0,1 % to £ 0,8%, preferred ³ 0,2 % to £ 0,5%.

The reaction can be carried out at ambient temperature, however also lower and higher temperatures are feasible. Preferred reaction temperatures are ³ 0 °C to £ 40 °C, with ³ 20 °C to £ 30 °C being preferred.

The aforementioned components, as well as the claimed components and the components to be used in accordance with the invention in the described embodiments, are not subject to any special exceptions with respect to their size, shape, material selection and technical concept such that the selection criteria known in the pertinent field can be applied without limitations.

Additional details, characteristics and advantages of the object of the invention are disclosed in the sub-claims and the following description of the respective examples -which in an exemplary fashio show preferred embodiments according to the invention. Such

embodiments do not necessarily represent the full scope of the invention, however, and reference is made therefore to the claims and herein for interpreting the scope of the invention. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the present invention as claimed.

In the figures:

Fig. 1 shows a molecular mass distribution diagram obtained by GPC elution of a polymer obtained by a polymerization according to a first embodiment of the present invention;

Fig. 2 shows a molecular mass distribution diagram obtained by GPC elution of a polymer obtained by a polymerization according to a second embodiment of the present invention;

Fig. 3 shows a molecular mass distribution diagram obtained by GPC elution of a polymer obtained by a polymerization according to a third embodiment of the present invention;

Fig. 4 shows a molecular mass distribution diagram obtained by GPC elution of a polymer obtained by a polymerization according to a fourth embodiment of the present invention; and

Fig. 5 shows a molecular mass distribution diagram obtained by GPC elution of a polymer obtained by a polymerization according to a fifth embodiment of the present invention;

Materials and methods:

¹H, ¹³C and ¹⁹F NMR spectra were recorded either on Varian V-NMRS 600, Varian V- NMRS 400 or Varian Mercury 300 spectrometer. 'H and ¹³C spectra are referenced to residual solvent signals; CDCb 7.26 ppm for 'H and 77.0 ppm for ¹³C. Coupling constants (7) are reported in Hz and coupling patterns are described as br = broad, s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet.

Toluene, THF, hexane and DCM were dried by solvent purification system (Innovative Technology PS-MD-5). Unless stated otherwise, other anhydrous solvents as well as all starting materials, ligands were commercially available and used as received. Solvents used for column chromatography (pentane, hexane, ethyl acetate and DCM) were received in technical grade and distilled prior to use. Unless otherwise stated, all reagentsand starting materials were purchased at reagent grade and used as received. Pd(I) dimer^[1] were prepared according to literature procedures.

Molecular weights (M_n,SEC and M_W,SEC) and molecular weight distributions (M_w/M_n) were determined by size-exclusion chromatography (SEC). SEC analyses were carried out with tetrahydrofuran (THF) (³99.7%, unstabilized, HiPerSolv CHROMANORM® HPLC grade, VWR) as eluent.

SEC was performed using a HPLC pump (PU-2080plus, Jasco) equipped with a refractive index detector (RI-2031plus, Jasco). The sample solvent contained 250 mg-mL^-1 3,5-di-tert-4- butylhydroxytoluene (BHT, ³99%, Fluka) as internal standard. One pre-column (8x50 mm) and four SDplus gel columns (8x300 mm, SDplus, MZ Analysentechnik) were applied at a flow rate of 1.0 mL-rnin^-1 at 20 °C. The diameter of the gel particles measured 5 mm, the nominal pore widths were 50, 10², 10³ and 10⁴ A. Calibration was achieved using narrow distributed poly(methyl methacrylate) standards (Polymer Standards Service). Results were evaluated using the PSS WinGPC UniChrom software (Version 8.1.1).

General polymerization method: The monomer (0.5 mmol, 1.0 equiv.) was placed into a Schlenk flask equipped with a magnetic stirrerbar, the flask was sealed with a rubber septum and was evacuated and back- filled with argon. Dry THF (5 ml) was then added and the solution was cooled to -78°C. nBuLi (0.19 ml of 2.5M solution in hexane, 0.475 mmol, 0.95 equiv.) was added drop-wise and the mixture was stirred for 1 hour at -78°C followed by the addition of a solution of ZnCE (0.55 ml, 1.0M in THF, 0.55 mmol, 1.1 equiv.). The reaction mixture was allowed to reach ambient temperature within 30 min. Then, Palladium (I) dimer catalyst ([Pd(m-I)(PtBu3)]2, 2.2 mg, 0.0025 mmol, 0.5 mol%) was added. Samples were taken via syringe after respective polymerization times and quickly quenched by adding them to methanol containing few drops of concentrated HC1. Crude reaction mixtures were washed with methanol (unless stated otherwise), then extracted with chloroform and analyzed by GPC and 'H NMR.

EXAMPLE I:

Example I

Example I refers to poly[9,9-bis(2-ethylhexyl)fluorene-2,7-diyl which was made from 9,9-Di- (2'-ethylhexyl)-2,7-dibromofluorene according to the general method above. The title product was obtained after purification by Soxhlett (washed with methanol, acetone and extracted with chloroform) as a yellow solid. 68 mg (87%). ¹H NMR (400 MHz, CDC1₃) d 7.80 (d, J = 8.1 Hz, 2H), 7.64 (s, 4H), 2.10 (s, 2H), 0.89 (s, 20H), 0.67 (d, j = 6.2 Hz, 6H), 0.57 (d, j = 7.2 Hz, 6H). Fig. 1 shows the molecular mass distribution curve of the polymer after a reaction time of 120 seconds.

This reaction was further investigated with different catalyst concentrations. The results can be seen in Table I.

Table I

EXAMPLE II:

Example II refers to Poly(2,5-bis(hexyloxy)phenylene which was made according to the general procedure from 1,4-dibromo-2,5-bis(hexyloxy)benzene. The product was obtained after purification by Soxhlett (washed with methanol and extracted with chloroform) as a white solid. 11 mg (20%). ¹H NMR (400 MHz, CDC1₃) d 7.10 (s, 2H), 3.92 (m, 4H), 1.68 (m, 4H) 1.40-1.21 (m, 12H), 0.87 (m, 6H).

Fig. 2 shows the molecular mass distribution curve of the polymer after a reaction time of 30 seconds.

EXAMPLE III:

Example II refers to Poly 2,7-dibromo-9-octyl-9H-carbazole which was made from 2,7- dibromo-9-octyl-9H-carbazole according to the general method above. The title product was obtained after purification by Soxhlett (washed with methanol and extracted with chloroform) as a yellow solid. 61 mg (74%). ¹H NMR (600 MHz, CDC1₃) d 8.25 (d, j = 17.2 Hz, 2H), 7.93 (s, 1H), 7.75 (s, 1H), 7.63 (s, 2H), 4.76 (s, 1H), 2.47 (s, 2H), 2.08 - 2.07 (s, 2H), 1.37

1.13 (m, 24H), 0.81 (t, j = 7.1 Hz, 6H).

Fig. 3 shows the molecular mass distribution curve of the polymer after a reaction time of 120 seconds.

EXAMPLE IV:

Example IV refers to Poly(9,9-dioctylfluorene) which was prepared from 2,7- dibromo-9,9- dioctylfluorene following the general method.. The title product was obtained after purification by Soxhlett (washed with methanol, acetone and extracted with chloroform) as a white solid. 65 mg (82%). NMR (400 MHz, CDC1₃) d 7.85-7.82 (m, 2H), 7.76-7.58 (m, 4H), 2.11 (m, 4H,), 1.22-1.02 (m, 20H), 0.81 (m, 10H).

Fig. 4 shows the molecular mass distribution curve of the polymer after a reaction time of 30 seconds.

This reaction was further investigated using different catalyst concentrations. The results are shown in Table II

EXAMPLE V:

Example V refers to Poly{2,7-[9,9-bis(4-hexyloxyphenyl)fluorene] } which was prepared from 2,7- dibromo-9,9-bis(4-hexyloxyphenyl)fluorene according to the general method. The title product was obtained after purification by Soxhlett (washed with methanol and extracted with chloroform) as a white solid. 78 mg (74%). ¾ NMR (600 MHz, CDC1₃) d 7.74 (d, / = 8.1 Hz, 2H), 7.56 - 7.50 (m, 4H), 7.15 (d, j = 8.6 Hz, 4H), 6.75 (d, j = 8.4 Hz, 4H), 3.88 (m, 4H), 1.72 (m, 4H), 1.41 (s, 4H), 1.34 - 1.24 (m, 8H), 0.88 (m, 6H). Fig. 5 shows the molecular mass distribution curve of the polymer after a reaction time of 60 seconds.

EXAMPLE VI

Example VI refers to 2,5-dibromo-3-hexylthiophene which was made as follows:

2,5-dibromo-3-hexylthiophene (0.5 mmol, 163 mg, 1.0 equiv.) was placed into a Schlenk flask equipped with a magnetic stirrer bar, the flask was sealed with a rubber septum and was evacuated and back-filled with argon. Dry THF (5 ml) was then added and the solution was cooled to -78°C. nBuLi (0.19 ml of 2.5M solution in hexane, 0.475 mmol, 0.95 equiv.) was added drop- wise and the mixture was stirred for 1 hour at -78°C followed by the addition of a solution of ZnC1₂ (0.55 ml, 1.0M in THF, 0.55 mmol, 1.1 equiv.). The reaction mixture was allowed to reach ambient temperature within 30 min. Then, Palladium (I) dimer catalyst ([Pd(m-I)(P/Bu3)]2, 2.18 mg, 0.0025 mmol, 0.5 mol%) was added and the mixture was allowed to react for 2 min, subsequently quenched by adding to a vial containing methanol and a few drops of concentrated HC1. The reaction mixture was then washed with methanol and acetone during 24 h (by Soxhlett), then extracted with chloroform to yield poly(3-hexylthiophene) as a green solid. 55 mg (65%). ¹H NMR (400 MHz, CDC1₃) d 6.98 (s, 1 H), 2.80 (t, 2 H), 1.70 (m, 2 H), 1.43 (m, 2 H), 1.34 (m, 4H), 0.91 (t, 3 H). These data are in agreement with those reported previously in the literature (X. Shi, A. Sui, Y. Wang, Y. Li, Y. Geng, F. Wang, Chem Commun 2015, 51, 2138-2140)

The particular combinations of elements and features in the above detailed embodiments are exemplary only; the interchanging and substitution of these teachings with other teachings in this and the patents/applications incorporated by reference are also expressly contemplated.

As those skilled in the art will recognize, variations, modifications, and other implementations of what is described herein can occur to those of ordinary skill in the art without departing from the spirit and the scope of the invention as claimed. Accordingly, the foregoing description is by way of example only and is not intended as limiting. In the claims, the word "comprising" does not exclude other elements or steps, and the indefinite article "a" or "an" does not exclude a plurality. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measured cannot be used to advantage. The invention's scope is defined in the following claims and the equivalents thereto. Furthermore, reference signs used in the description and claims do not limit the scope of the invention as claimed.

Claims

1. A polymerization method, including a chain-prolongating step of forming a carbon-carbon-bond between a sp² or sp-hybridized carbon with an at least formally nucleophilic leaving group and a sp² or sp-hybridized carbon with an at least formally electrophilic leaving group in the presence of a Pd(I)- compound.

2. The method according to Claim 1, whereby the polymerization method

comprises the polymerization of aromatic, heteroaromatic, alkenyl or alkinyl molecules.

3. The method according to Claim 1 or 2, whereby the nucleophilic leaving group is selected from halides, pseudohalides, organic and inorganic ethers and esters

4. The method according to any of the claims 1 to 3, whereby the electrophilic leaving groups is selected from metals or - when the metal has an at least formal oxidation state of greater than (I) - metal compounds of the structure MR_x with M being the metal, R being an at least formally nucleophilic leaving group and x being 1 or greater but smaller than the (formal) oxidation state of the metal M.

5. The method according to any of the claims 1 to 4, whereby the Pd(I)- compound comprises an electron-donating ligand.

6. The method according to any of the claims 1 to 5, whereby the Pd(I)- compound comprises a phosphine or carbene ligand.

7. The method according to any of the claims 1 to 6, whereby the Pd(I) compound is dimeric

8. The method according to any of the claims 1 to 7, whereby the Pd(I)- compound comprises a compound with the following structure:

With R¹ and R² being independent from each other electron donating ligands, especially phosphines and/or carbenes and R³ and R⁴ independently from each other halogen or pseudohalogen.

9. The method according to any of the claims 1 to 8, whereby one of R³ and R⁴ is iodide.

10. The method according to any of the claims 1 to 9, whereby both of R³ and R⁴ are iodide.

11. The method according to any of the claims 1 to 10, whereby R³ and/or R⁴ are iodide and R¹ = R²

12. The method according to any of the claims 1 to 11, whereby R³ and R⁴ are iodide and R¹ = R²

13. The method according to any of the claims 1 to 12, whereby R³ and R⁴ are iodide and R¹ and R² are phosphine.

14. The method according to any of the claims 1 to 13, whereby the content of the Pd(I)-compound (in mol% based on the alkene to be isomerized prior to the reaction) is ³ 0.05 % to £ 1%.

15. The method according to any of the claims 1 to 14, whereby the method is carried out at ³ 0 °C to £ 40 °C