Phosphines Bearing Alkyne Substituents: Synthesis and Hydrophosphination Polymerization

被引：12

作者：

Greenberg, Sharonna ^{[1
]}

Stephan, Douglas W. ^{[1
]}

机构：

[1] Univ Toronto, Dept Chem, Toronto, ON M5S 3H6, Canada

来源：

INORGANIC CHEMISTRY | 2009年 / 48卷 / 17期

基金：

加拿大自然科学与工程研究理事会;

关键词：

LIVING ANIONIC-POLYMERIZATION; RING-OPENING POLYMERIZATION; INTRAMOLECULAR HYDROPHOSPHINATION/CYCLIZATION; CATALYTIC SYNTHESIS; CRYSTAL-STRUCTURE; PRIMARY PNICTANES; COMPLEXES; COPPER(I); POLYMERS; BONDS;

D O I：

10.1021/ic9012284

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A synthetic route is described for a series of phosphines bearing pendant alkyne substituents, from the conversion of BrC6H2R2C CR' (R = Me, i-Pr; R' = Ph, SiMe3) to [(mu-Br)Cu(Et2N)(2)PC6H2R2C CR'](2) and subsequently to Cl2PC6H2R2C CR' and H2PC6H2R2C CR'. Lithiation and subsequent alkylation yield the secondary phosphines R(H)PC6H2(i-Pr)(2)C CPh (R = CH(2)i-Pr, CH2Ph). Intermolecular hydrophosphination-polymerization is used to prepare the polymeric species [RPC6H2(i-Pr)(2)CH=CPh](n), which can then be sulfurized to give [RP(S)C6H2(i-Pr)(2)CH=CPh](n). The polymeric products were characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and gel permeation chromatography. These data indicate a degree of polymerization (DPn) Of up to 60. Discussion of the mechanism is augmented with gas-phase density functional theory calculations.

引用

页码：8623 / 8631

页数：9

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