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Polymerization of 1-chloro-2-phenylacetylene by cationic monoanionic tridentate (S,S)-bis(oxazolinylphenyl)amido-ligated palladium catalysts: is it a coordination–insertion mechanism?†
Polymer Chemistry ( IF 4.1 ) Pub Date : 2018-08-31 00:00:00 , DOI: 10.1039/c8py00903a
Xiaolu Wu 1, 2, 3, 4, 5 , Zhi Yang 1, 2, 3, 4, 5 , Xinwen Yan 1, 2, 3, 4, 5 , Pengfei Zhang 1, 2, 3, 4, 5 , Lin Wang 3, 5, 6, 7 , Ge Guo 1, 2, 3, 4, 5 , Yuping Dong 3, 5, 7, 8, 9 , Xiaofang Li 1, 2, 3, 4, 5
Affiliation  

A series of air-stable monoanionic tridentate (S,S)-bis(oxazolinylphenyl)amido-ligated palladium (Pd) chloride complexes (R2-(S,S)-BOPA)PdCl (1a–e) (1a: R = Ph; 1b: R = iPr; 1c: R = Bn; 1d: R = Et; 1e: R = Me) have been synthesized and structurally characterized. The double decomposition reaction of these Pd chloride complexes 1a–e with one equivalent of silver trifluoromethanesulfonate (AgOTf) quantitatively affords the corresponding cationic monoanionic tridentate Pd species [(R2-(S,S)-BOPA)Pd]+[OTf] (2a–e) as characterized by 1H and 13C NMR spectroscopy. Such single-component or in situ generated cationic Pd species are active for the polymerization of once used 1-chloro-2-phenylacetylenes (CPAs) bearing nonpolar, halogen, and polar substituents (3a: Cl–C[triple bond, length as m-dash]C–C6H4p-Me; 3c: Cl–C[triple bond, length as m-dash]C–C6H5; 3e: Cl–C[triple bond, length as m-dash]C–C6H4p-F; 3f: Cl–C[triple bond, length as m-dash]C–C6H4p-Cl; 3h: Cl–C[triple bond, length as m-dash]C–C6H4p-NO2; 3j: Cl–C[triple bond, length as m-dash]C–C6H4p-COCH3) even in air, affording partly soluble cis-selective poly(1-chloro-2-phenylacetylene)s (PCPAs) with high molecular weights and broad molecular weight distributions similar to those obtained by the known Pd catalysts. More significantly, the single-component cationic Pd species can also promote the polymerization of unused CPAs (3b: Cl–C[triple bond, length as m-dash]C–C6H4m-Me; 3d: Cl–C[triple bond, length as m-dash]C–C6H4p-OMe; 3g: Cl–C[triple bond, length as m-dash]C–C6H4p-COOEt; 3i: Cl–C[triple bond, length as m-dash]C–(1-C10H7)) for the first time, providing novel cis-selective PCPAs which are unavailable from traditional catalysts. Similar to the known Pd catalysts, a possible coordination–insertion mechanism is proposed by means of 1H NMR, IR, and ESI-MS spectroscopies, which provides a new insight into the initiation and termination polymerization process of CPAs catalyzed by these cationic monoanionic tridentate (S,S)-bis(oxazolinylphenyl)amido-ligated Pd catalysts.

中文翻译:

阳离子单阴离子三齿(SS)-双(恶唑啉基苯基)氨基连接的钯催化剂聚合1-氯-2-苯基乙炔:这是配位插入机制吗?

一系列空气稳定的单阴离子三齿(SS)-双(恶唑啉基苯基)氨基连接的氯化钯(Pd)络合物(R 2-SS)-BOPA)PdCl(1a–e)(1a:R = Ph值;图1b:R =镨; 1C:R = BN; 1D:R =的Et; 1E:R = Me)的已合成和结构表征。这些Pd氯化物络合物1a–e与一当量的三氟甲磺酸银(AgOTf)的双分解反应定量提供了相应的阳离子单阴离子三齿Pd物质[(R 2-(SS)-BOPA)Pd] + [OTf] -2a–e)的特征在于1 H和13 C NMR光谱学。这种单组分或原位生成的阳离子Pd物种对于曾经使用过的带有非极性,卤素和极性取代基的1-氯-2-苯基乙炔(CPA)的聚合具有活性(3a:Cl–C [三重键,长度为m-破折号]C–C 6 H 4p -Me;图3c值:Cl-C [三重键,长度为m-破折号]C-C 6 H ^ 5 ; 3E:氯-C [三重键,长度为m-破折号]C-C 6 H ^ 4 -p -F; 3f:Cl–C [三重键,长度为m-破折号]–C 6 H 4p -Cl;3H值:Cl-C [三重键,长度为m-破折号]C-C 6 H ^ 4 - p -NO 2 ; 3j:即使在空气中,Cl–C [三重键,长度为m-破折号]C–C 6 H 4p -COCH 3)也能部分溶解具有高分子量和宽分子量分布的顺式选择性聚(1-氯-2-苯基乙炔)(PCPAs)类似于通过已知的Pd催化剂获得的那些。更重要的是,单组分阳离子Pd物质还可以促进未使用的CPA的聚合(3b:Cl–C [三重键,长度为m-破折号]–C 6 H 4m -Me;3d:Cl–C [三重键,长度为m-破折号]–C 6 H 4p -OMe;3g:Cl–C [三重键,长度为m-破折号]–C 6 H 4p -COOEt;3i:Cl–C [三重键,长度为m-破折号]C–(1-C 10 H 7))首次提供了传统催化剂无法提供的新型顺式选择性PCPA。类似于已知的钯催化剂,一种可能的配位-插入机构,提出借助于11 H NMR,IR和ESI-MS光谱学,为这些阳离子单阴离子三齿(SS)-双(恶唑啉基苯基)酰胺基连接的Pd催化剂催化的CPA的引发和终止聚合过程提供了新的见解。
更新日期:2018-08-31
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