The Addition Polymerization of a PC Bond:  A Route to New Phosphine Polymers

Tsang, Chi‐Wing; Yam, Mandy; Gates, Derek P.

doi:10.1021/ja029120s

Cited by 134 publications

(115 citation statements)

References 19 publications

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“…(84)]. [305] The initiator (CH 3 OTf (OTf = CF 3 SO 3 ) or CH 3 I) initially gives a phosphiranium salt which is then attacked by the phosphorus [ 351] By analogy with the thoroughly investigated polypyrroles and polythiophenes which provide very interesting n-or pdoped electroconducting organic materials, it is tempting to investigate the synthesis of polyphospholes. Several recent DFT studies [306][307][308] have demonstrated that a-connected polyphospholes should be good substrates for making efficient organic conductors.…”

Section: Molecular Materialsmentioning

confidence: 99%

Phospha‐Organic Chemistry: Panorama and Perspectives

2003

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Since the beginning of the seventies, organophosphorus chemistry has been completely rejuvenated by the discovery of stable derivatives in which phosphorus has the coordination numbers one or two. The chemistry of these compounds mimics the chemistry of their all-carbon analogues. In this Review article this analogy is discussed for the phosphorus counterparts of alkenes, alkynes, and carbenes. In each case, the synthesis, reactivity, and coordination modes are briefly examined. Some special electronic configurations are also discussed, which include one-electron Pbond;P bonds, strained bonds, and aromatic systems. To conclude, some potential applications of this chemistry in the areas of molecular materials and homogeneous catalysis are presented.

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Section: Molecular Materialsmentioning

confidence: 99%

Phospha‐Organic Chemistry: Panorama and Perspectives

2003

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“…[6] For the present copolymerization studies, we favored conventional radical over anionic initiation methods, since they are convenient to perform and do not have the same strict purity requirements of anionic polymerization. Therefore, we decided to investigate the copolymerization of 1 and styrene with 1,1'-azobis(cyclohexanecarbonitrile) [VAZO, catalyst 88] as the free-radical source.…”

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confidence: 99%

Radical Copolymerization of a Phosphaalkene with Styrene: New Phosphine‐Containing Macromolecules and Their Use in Polymer‐Supported Catalysis

et al. 2004

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Since Beckers synthesis of the first stable phosphaalkene in 1976, [1] these compounds, which contain a P=C bond and were once considered exotic, now constitute a major branch of phosphorus chemistry. Applications for these compounds are even being developed.[2-4] The ability of P = C bonds, in many instances, to "copy" the well-established chemistry of isolobal C=C bonds has attracted considerable attention. [2, 3a, d] In molecular chemistry, the remarkable analogy between phosphaalkenes and alkenes is evidenced by phospha variants of a number of reactions, including 1,2-addition, [4+2]cycloaddition, Peterson and Wittig olefination, h 2 coordination to metal centers, and Cope and allylic rearrangements. One of the most important reactions of C = C bonds is the addition polymerization of olefins, which is used to produce many commodity polymers. The absence of an analogous polymer chemistry for P=C bonds prompted us to investigate addition polymerization as a potential route to new phosphine polymers. We recently reported the first addition polymerization of the phosphaalkene 1[5] (Mes = 2,4,6-trimethylphenyl) to give the poly(methylenephosphine) 2 (M w % 10 4 g mol À1 by GPC versus polystyrene), an alternating PÀC polymer. [6]

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“…In a separate study, a stable phosphaalkene 19 that was less likely to undergo intramolecular C-H activation was studied [85]. This monomer can be prepared using based induced dehydrochlorination [44] or following a phosphaPeterson route [50,86].…”

Section: Poly(methylenephosphine)smentioning

confidence: 99%