Ambient‐Temperature Living Anionic Polymerization of Phosphaalkenes: Homopolymers and Block Copolymers with Controlled Chain Lengths

Noonan, Kevin J. T.; Gates, Derek P.

doi:10.1002/ange.200602955

Cited by 32 publications

(12 citation statements)

References 49 publications

(16 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Our studies showed that MesPCPh 2 ( 1 ) and related monomers polymerize in the presence of radical or anionic initiators to afford poly(methylenephosphine) (Scheme ) 6. The living anionic polymerization of 1 permits the formation of functional phosphine‐containing block copolymers,7, 8 and the radical‐initiated copolymerization of 1 with styrene affords random copolymers 9…”

Section: Methodsmentioning

confidence: 88%

Isomerization Polymerization of the Phosphaalkene MesPCPh₂: An Alternative Microstructure for Poly(methylenephosphine)s

et al. 2013

Self Cite

View full text Add to dashboard Cite

The synthesis and study of main-group-element analogues of alkenes and alkynes containing genuine (p À p)p bonds involving p-block elements is a central theme of inorganic chemistry. [1,2] The prospect to "copy" the predictable and sophisticated reaction chemistry of C=C and CC bonds utilizing functional inorganic systems is particularly enticing. However, in many instances, the investigation of multiple bonds of heavy elements leads to fascinating, albeit unexpected, outcomes that reinforce the fundamental differences between the first and subsequent periods.Inspired by the intriguing analogy between P=C and C=C bonds in molecular chemistry, [3] we developed the addition polymerization of phosphaalkenes as a route to new functional phosphorus-containing polymers (Scheme 1). [4] Although the synthesis of phosphorus-containing macromolecules is of widespread interest because of their attractive properties and potential applications, [5] the study of the addition polymerization of P = C bonds remains in its infancy. Our studies showed that MesP=CPh 2 (1) and related monomers polymerize in the presence of radical or anionic initiators to afford poly(methylenephosphine) (Scheme 1). [6] The living anionic polymerization of 1 permits the formation of functional phosphine-containing block copolymers, [7,8] and the radical-initiated copolymerization of 1 with styrene affords random copolymers. [9] In order to explore the mechanism of radical addition to P = C bonds during polymerization, we investigated the reactions of monomer 1 with TEMPO-derived radical sources. Herein, we report the discovery of a fascinating isomerization polymerization of phosphaalkene 1 in the presence of radical alkoxyamine initiators. These striking results led to a revision of the proposed microstructure for poly(methylenephosphine) that was produced by a radical reaction.In an effort to understand the initiation step in the radical polymerization of 1, we investigated its reaction with TEMPO (1-2 equiv). 31 P NMR spectroscopic analysis of the reaction mixtures suggested the formation of multiple products, including radical species, which were detected by EPR spectroscopy. To date, none of these products have been successfully isolated or unambiguously identified. In contrast, employing the complex 1·AuCl [10,11] instead of 1 affords a single product with TEMPO. Specifically, treatment of a solution of 1·AuCl in toluene with TEMPO (1 equiv) resulted in 50 % conversion of 1·AuCl (d = 167.1) to a new species, as determined by 31 P NMR spectroscopy. Addition of more TEMPO (1 equiv, that is, 2 equiv total) resulted in complete conversion of 1·AuCl to two products in a ratio of approximately 1:3, which displayed 31 P signals at 135.6 ppm (d, J PH = 18 Hz) and 130.5 ppm (d, J PH = 18 Hz). The magnitudes of the 31 P-1 H coupling constants are not consistent with the expected product Mes(TEMPO)P(AuCl)-C-(TEMPO)Ph 2 .Colorless crystals were obtained by slow diffusion of hexanes into the reaction mixture at À30 8C. Analysis of the crystals by X-ray crys...

show abstract

Section: Methodsmentioning

confidence: 88%

Isomerization Polymerization of the Phosphaalkene MesPCPh₂: An Alternative Microstructure for Poly(methylenephosphine)s

et al. 2013

Self Cite

View full text Add to dashboard Cite

show abstract

“…Phosphorus has been well‐known as ‘carbon analog’, however phosphorus‐based oligomers or polymers are much less reported . Gates et al . and Protasiewicz et al .…”

Section: Background and Originality Contentmentioning

confidence: 99%

Zig‐Zag Diphosphene Oligomers Linked by Silver(I) Cation

et al. 2020

View full text Add to dashboard Cite

Summary of main observation and conclusion The coordination of silver cation to diphosphene Mes*P=PMes* (1, Mes* = tBu3C6H2) was investigated in detail. The reaction of 1 with Ag[Al(ORF)4] (ORF = OC(CF3)3) in the ratios of 2 : 1, 3 : 2 and 1 : 2 led to the formation of the first cationic silver linked diphosphene complexes 2—4. Complexes 2 and 3 contain two and three diphosphene molecules linked by the linear Ag(I) cation, respectively, and they feature unusual zig‐zag topologies. Complex 4 is a dinuclear silver complex, and each Ag(I) center features a tetrahedral geometry, coordinated by one phosphorus atom of diphosphene 1 and three chloro atoms of two CH2Cl2 molecules.

show abstract

“…Ein entscheidender Durchbruch wurde kürzlich erzielt, als Noonan und Gates nachweisen konnten, dass Phosphaalkene in Gegenwart von Organolithium‐Initiatoren durch lebende anionische Polymerisation bei Umgebungsbedingungen umgesetzt werden 21. Die Reaktion ist völlig analog zur Polymerisation von Olefinen wie Styrol 21. Auf diese Weise gelang die Synthese von Poly(methylenphosphanen) mit kontrollierbaren Molekulargewichten (steuerbar über das Verhältnis Monomer/Initiator) und engen Molekulargewichtsverteilungen.…”

Section: Besondere Funktionalitäten Von Blockcopolymeren Die Aus Demunclassified

Blockcopolymere mit funktionellen anorganischen Blöcken: lebende Additionspolymerisation von anorganischen Monomeren

Manners

2007

Angewandte Chemie

View full text Add to dashboard Cite

Auch Anorganisches will leben: Die lebende Polymerisation anorganischer Monomere bietet einen Zugang zu Blockcopolymeren, die in dünnen Filmen oder bestimmten Lösungsmitteln selbstorganisieren und Nanodomänen mit anorganischen Komponenten bilden können. Ein wichtiger Fortschritt auf diesem Gebiet ist die lebende anionische Additionspolymerisation von Phosphaalkenen, über die jüngst berichtet wurde (siehe Schema; Mes=2,4,6‐Me3C6H2).

show abstract

Ambient‐Temperature Living Anionic Polymerization of Phosphaalkenes: Homopolymers and Block Copolymers with Controlled Chain Lengths

Cited by 32 publications

References 49 publications

Isomerization Polymerization of the Phosphaalkene MesPCPh₂: An Alternative Microstructure for Poly(methylenephosphine)s

Isomerization Polymerization of the Phosphaalkene MesPCPh₂: An Alternative Microstructure for Poly(methylenephosphine)s

Zig‐Zag Diphosphene Oligomers Linked by Silver(I) Cation

Blockcopolymere mit funktionellen anorganischen Blöcken: lebende Additionspolymerisation von anorganischen Monomeren

Contact Info

Product

Resources

About

Ambient‐Temperature Living Anionic Polymerization of Phosphaalkenes: Homopolymers and Block Copolymers with Controlled Chain Lengths

Cited by 32 publications

References 49 publications

Isomerization Polymerization of the Phosphaalkene MesPCPh2: An Alternative Microstructure for Poly(methylenephosphine)s

Isomerization Polymerization of the Phosphaalkene MesPCPh2: An Alternative Microstructure for Poly(methylenephosphine)s

Zig‐Zag Diphosphene Oligomers Linked by Silver(I) Cation

Blockcopolymere mit funktionellen anorganischen Blöcken: lebende Additionspolymerisation von anorganischen Monomeren

Contact Info

Product

Resources

About

Isomerization Polymerization of the Phosphaalkene MesPCPh₂: An Alternative Microstructure for Poly(methylenephosphine)s

Isomerization Polymerization of the Phosphaalkene MesPCPh₂: An Alternative Microstructure for Poly(methylenephosphine)s