Polymerization of l‐(pentafluorophenyl)‐<scp>L</scp>‐alkynes by Ta and Nb catalysts

Yoshimura, Toshio; Masuda, Toshio; Higashimura, Toshinobu; Ishihara, Takashi

doi:10.1002/pola.1986.080241236

Cited by 10 publications

(5 citation statements)

References 7 publications

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“…We have also examined the reactivities of complexes 7 , 8 , and 9 with phenylacetylene for the following reason. Previous studies 10,17 have shown that combining the precursors (1-Me-indenyl)Ni(PR 3 )X (R = Ph or Cy, X = Cl, Me, CCPh, thienyl) with methylaluminoxane (MAO) forms catalytically active species that polymerize phenylacetylene to cis,transoidal -poly(phenylacetylene) (PPA); this material is of interest for applications requiring nonlinear optical and magnetic susceptibilities, photoconductivity, and gas permeability . Although the interaction of MAO with these precursors gives rise to cationic species, the role of the latter in the polymerization reaction has not been established with certainty.…”

Section: Resultsmentioning

confidence: 99%

“…We were intrigued to find, however, that polymerization reactions using combinations of MAO and independently prepared (as opposed to in situ formed) samples of the Ni-Me and Ni−CCPh derivatives 4 and 5 , respectively, yielded PPA samples with much lower M w values (e.g., see run 11 for the reaction of 5 + MAO). Since the combination of MAO and the analogous neutral Ni−R derivatives (R = Me or CCPh) bearing nonfunctionalized Ind ligands polymerize phenylacetylene, , it is clear that the amine moiety has a detrimental effect on these reactions. We conclude, therefore, that the cationic species cannot polymerize phenylacetylene in the absence of MAO, but the precise role of the latter in these reactions remains unknown.…”

Section: Resultsmentioning

confidence: 99%

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Aminoalkyl-Substituted Indenylnickel(II) Complexes (η³:η⁰-Ind(CH₂)₂NMe₂)Ni(PR₃)X and [(η³:η¹-Ind(CH₂)₂NMe₂)Ni(PR₃)][BPh₄]: Influence of the Phosphine in Ligand Exchange and Polymerization Reactions

Groux

Zargarian

2003

Organometallics

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Reaction of LiInd(CH 2 ) 2 NMe 2 with (PR 3 ) 2 NiCl 2 gave the neutral complexes (η 3 :η 0 -Ind(CH 2 ) 2 -NMe 2 )Ni(PR 3 )Cl (R ) Ph (1) or Me (2)), while the PCy 3 analogue, (η 3 :η 0 -Ind(CH 2 ) 2 NMe 2 )-Ni(PCy 3 )Cl (3), was obtained by reacting 1 with PCy 3 . These Ni-Cl species react with R′Li or NaBPh 4 to form, respectively, the corresponding Ni-R′ derivatives (η 3 :η 0 -Ind(CH 2 ) 2 NMe 2 )-Ni(PR 3 )R′ (R ) Ph, R′ ) Me (4) or CCPh (5); R ) R′ ) Me ( 6)) or the cationic species [(η 3 : 7), Me (8), or Cy ( 9)), in which the NMe 2 moiety is coordinated to the nickel center. These complexes have been fully characterized, including solid state structure determinations by X-ray crystallography for complexes 2, 4, 5, 6, and 9. Inspection of the structural data showed that replacing the Cl ligand by the more strongly donating ligands CCPh and Me reinforces the Ni-P and Ni-Ind interactions. On the other hand, electrochemical measurements showed that the reduction potentials of the Ni-Cl compounds are intermediate between the Ni-R′ derivatives, which are more resistant to reduction, and the cationic species, which are the easiest to reduce. The cationic complexes are single-component catalysts for the polymerization of styrene, giving poly(styrene) with M w in the range of 10 4 -10 5 , and the hydrosilylation of styrene and 1-hexene with PhSiH 3 and Ph 2 SiH 2 . The nature of the phosphine ligand has an important influence on the catalytic reactivities, the PMe 3 analogue 8 being the most active catalyst.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Aminoalkyl-Substituted Indenylnickel(II) Complexes (η³:η⁰-Ind(CH₂)₂NMe₂)Ni(PR₃)X and [(η³:η¹-Ind(CH₂)₂NMe₂)Ni(PR₃)][BPh₄]: Influence of the Phosphine in Ligand Exchange and Polymerization Reactions

Groux

Zargarian

2003

Organometallics

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“…Often, the syntheses of these polymers are neither facile nor high yielding. Furthermore, despite the current interest in fluorinated polymers, few conjugated materials have been prepared that contain the considerably more electron-withdrawing perfluorophenyl group as a substituent, , and simple methodologies for the preparation of perfluoroaryl-substituted conjugated polymers and oligomers are not well developed.…”

Section: Introductionmentioning

confidence: 99%

Regioselective Coupling of Pentafluorophenyl Substituted Alkynes: Mechanistic Insight into the Zirconocene Coupling of Alkynes and a Facile Route to Conjugated Polymers Bearing Electron-Withdrawing Pentafluorophenyl Substituents

et al. 2003

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The reaction of Cp(2)ZrCl(2) with 2 equiv of BuLi at -78 degrees C, followed by the addition of an unsymmetrical tetra- or pentafluorophenyl substituted alkyne R(1)C[triple bond]CAr(f) (R(1), Ar(f) = (CH(2))(4)Me, p-C(6)F(4)H; Me, p-C(6)F(4)H; Ph, C(6)F(5)), resulted in regioselective couplings of these alkynes to zirconacyclopentadienes in which the Ar(f) substituents preferentially adopt the 3,4-positions (beta beta) of the zirconacyclopentadiene ring. With Cp(2)Zr(py)(Me(3)SiC[triple bond]CSiMe(3)) as the zirconocene reagent, the couplings could be carried out at room temperature; however, at higher temperatures significant quantities of the 2,4-fluoroaryl substituted (alpha beta) isomers were also formed. None of the conditions employed produced the 2,5-fluoroaryl substituted (alpha alpha) isomers. These fluoroaryl-substituted zirconacyclopentadienes were readily converted to butadienes via reactions with acids. The zirconacyclopentadiene Cp(2)ZrC(4)-2,5-Ph(2)-3,4-(C(6)F(5))(2), which resulted from the coupling of PhC[triple bond]C(C(6)F(5)), was converted to the corresponding thiophene by reaction with S(2)Cl(2), and to an arene by reaction with MeO(2)CC[triple bond]CCO(2)Me/CuCl. Mechanistic studies on zirconocene couplings of (p-CF(3)C(6)H(4))C[triple bond]C(p-MeC(6)H(4)) indicate that the observed regioselectivities are determined by an electronic factor that controls the orientation of at least one of the two alkynes as they are coupled. Additionally, these studies suggest an unsymmetrical transition state for the zirconocene coupling of alkynes, and this is supported by DFT calculations. The reaction of [(C(6)F(5))C[triple bond]CCH(2)](2)CH(2) with Cp(2)Zr(py)(Me(3)SiC[triple bond]CSiMe(3)) resulted in a zirconacyclopentadiene in which the pentafluorophenyl substituents have been forced into the 2,5-positions (alpha alpha). Zirconocene coupling of the diyne (C(6)F(5))C[triple bond]C-1,4-C(6)H(4)-C[triple bond]C(C(6)F(5)) provided a route to conjugated polymers bearing electron-withdrawing pentafluorophenyl groups.

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“…A number of substituted polyacetylenes have been synthesized by using group 5 x 106]. This is quite interesting because the Mw of poly-CPA) itself is usually no more than 3 X 104.…”

Section: Introductionmentioning

confidence: 99%

Polymerization of (pentafluorophenyl)acetylene and (p-butyl-o,o,m,m-tetrafluorophenyl)acetylene and polymer properties

Yoshimura¹,

Masuda²,

Higashimura³

et al. 1991

Macromolecules

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Polymerization of l‐(pentafluorophenyl)‐L‐alkynes by Ta and Nb catalysts

Cited by 10 publications

References 7 publications

Aminoalkyl-Substituted Indenylnickel(II) Complexes (η³:η⁰-Ind(CH₂)₂NMe₂)Ni(PR₃)X and [(η³:η¹-Ind(CH₂)₂NMe₂)Ni(PR₃)][BPh₄]: Influence of the Phosphine in Ligand Exchange and Polymerization Reactions

Aminoalkyl-Substituted Indenylnickel(II) Complexes (η³:η⁰-Ind(CH₂)₂NMe₂)Ni(PR₃)X and [(η³:η¹-Ind(CH₂)₂NMe₂)Ni(PR₃)][BPh₄]: Influence of the Phosphine in Ligand Exchange and Polymerization Reactions

Regioselective Coupling of Pentafluorophenyl Substituted Alkynes: Mechanistic Insight into the Zirconocene Coupling of Alkynes and a Facile Route to Conjugated Polymers Bearing Electron-Withdrawing Pentafluorophenyl Substituents

Polymerization of (pentafluorophenyl)acetylene and (p-butyl-o,o,m,m-tetrafluorophenyl)acetylene and polymer properties

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Polymerization of l‐(pentafluorophenyl)‐L‐alkynes by Ta and Nb catalysts

Cited by 10 publications

References 7 publications

Aminoalkyl-Substituted Indenylnickel(II) Complexes (η3:η0-Ind(CH2)2NMe2)Ni(PR3)X and [(η3:η1-Ind(CH2)2NMe2)Ni(PR3)][BPh4]: Influence of the Phosphine in Ligand Exchange and Polymerization Reactions

Aminoalkyl-Substituted Indenylnickel(II) Complexes (η3:η0-Ind(CH2)2NMe2)Ni(PR3)X and [(η3:η1-Ind(CH2)2NMe2)Ni(PR3)][BPh4]: Influence of the Phosphine in Ligand Exchange and Polymerization Reactions

Regioselective Coupling of Pentafluorophenyl Substituted Alkynes: Mechanistic Insight into the Zirconocene Coupling of Alkynes and a Facile Route to Conjugated Polymers Bearing Electron-Withdrawing Pentafluorophenyl Substituents

Polymerization of (pentafluorophenyl)acetylene and (p-butyl-o,o,m,m-tetrafluorophenyl)acetylene and polymer properties

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Aminoalkyl-Substituted Indenylnickel(II) Complexes (η³:η⁰-Ind(CH₂)₂NMe₂)Ni(PR₃)X and [(η³:η¹-Ind(CH₂)₂NMe₂)Ni(PR₃)][BPh₄]: Influence of the Phosphine in Ligand Exchange and Polymerization Reactions

Aminoalkyl-Substituted Indenylnickel(II) Complexes (η³:η⁰-Ind(CH₂)₂NMe₂)Ni(PR₃)X and [(η³:η¹-Ind(CH₂)₂NMe₂)Ni(PR₃)][BPh₄]: Influence of the Phosphine in Ligand Exchange and Polymerization Reactions