1,2,3-Triazole based bisphosphine, 5-(diphenylphosphanyl)-1-(2-(diphenylphosphanyl)-phenyl)-4-phenyl-1H-1,2,3-triazole: an ambidentate ligand with switchable coordination modes†,RSC Advances

当前位置： X-MOL 学术 › RSC Adv. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

1,2,3-Triazole based bisphosphine, 5-(diphenylphosphanyl)-1-(2-(diphenylphosphanyl)-phenyl)-4-phenyl-1H-1,2,3-triazole: an ambidentate ligand with switchable coordination modes†
RSC Advances ( IF 3.9 ) Pub Date : 2018-07-18 00:00:00 , DOI: 10.1039/c8ra04086a
Latchupatula Radhakrishna ₁ , Madhusudan K Pandey ₁ , Maravanji S Balakrishna ₁

Affiliation

The reaction of 1-(2-bromophenyl)-4-phenyl-1H-1,2,3-triazole (1) with Ph₂PCl yielded bisphosphine, 5-(diphenylphosphanyl)-1-(2-(diphenylphosphanyl)phenyl)-4-phenyl-1H-1,2,3-triazole (2). Bisphosphine 2 exhibits ambidentate character in either the κ²-P,N or κ²-P,P coordination mode. Treatment of 2 with [M(CO)₄(piperidine)₂] (M = Mo and W) yielded κ²-P,N and κ²-P,P coordinated Mo⁰ and W⁰ complexes [M(CO)₄(2)] [M = W-κ²-P,N (4); Mo-κ²-P,P (5); W-κ²-P,P (6)] depending on the reaction conditions. Formation and stability of κ²-P,P coordinated Mo⁰ and W⁰ complexes were assessed by time dependent ³¹P{¹H} NMR experiments and DFT studies. The complex 4 on treatment with [AuCl(SMe₂)] afforded the hetero-bimetallic complex [μ-PN,P-{o-Ph₂P(C₆H₄){1,2,3-N₃C(Ph)C(PPh₂AuCl)}-κ²-P,N}W(CO)₄] (7). The 1 : 1 reaction between 2 and [CpRu(PPh₃)₂Cl] yielded [(η⁵-C₅H₅)RuCl{o-Ph₂P(C₆H₄){1,2,3-N₃C(Ph)C(PPh₂)}}-κ²-P,P] (8), whereas the similar reaction with [Ru(η⁶-p-cymene)Cl₂]₂ in a 2 : 1 molar ratio produced a cationic complex [(η⁶-p-cymene)RuCl{o-Ph₂P(C₆H₄){1,2,3-N₃C(Ph)C(PPh₂)}}-κ²-P,N]Cl (9). Similarly, treatment of 2 with [M(COD)(Cl)₂] (M = Pd and Pt) in a 1 : 1 molar ratio yielded Pd^II and Pt^II complexes [{o-Ph₂P(C₆H₄){1,2,3-N₃C(Ph)C(PPh₂)}-κ²-P,P}PdCl₂] (10) and [{o-Ph₂P(C₆H₄){1,2,3-N₃C(Ph)C(PPh₂)}-κ²-P,P}PtCl₂] (11). The reaction of 2 with 2 equiv. of [AuCl(SMe₂)] afforded [Au₂Cl₂{o-Ph₂P(C₆H₄){1,2,3-N₃C(Ph)C(PPh₂)}}-μ-P,P] (12). Most of the complexes have been structurally characterized. Palladium complex 10 shows excellent catalytic activity towards Cu-free Sonogashira alkynylation/cyclization reactions.

中文翻译：

1,2,3-三唑基双膦，5-（二苯基膦基）-1-（2-（二苯基膦基）-苯基）-4-苯基-1 H -1,2,3-三唑：具有可切换配位模式的双齿配体†

1-（2-溴苯基）-4-苯基-1 H -1,2,3-三唑（1）与Ph ₂ PCl反应生成双膦，5-（二苯基膦基）-1-（2-（二苯基膦基）苯基）-4-苯基-1 H -1,2,3-三唑（2）。双膦2展品ambidentate字在任一κ ² -P，N或κ ² -P，P配位模式。的治疗2与[M（CO）₄（哌啶）₂ ]（M = Mo和W），得到κ ² -P，N和κ ² -P，P协调沫⁰和W ⁰络合物[M（CO）₄（2个）] [M = W-κ ² -P，N（4）; 的Mo-κ ² -P，P（5）; W-κ ² -P，P（6）]取决于反应条件。的κ形成和稳定性² -P，P协调沫⁰和W ⁰复合物经时间评估依赖³¹ p { ^1个H} NMR实验和研究DFT。用[AuCl（SMe ₂）]处理的配合物4提供了异双金属配合物[μ-PN，P- { o -Ph ₂ P（C ₆ H ₄）{1,2,3-N ₃ C（Ph ）C（PPh ₂AUCL）} - κ ² -P，N} W（CO）₄ ]（7）。在1：1之间反应2和[CPRU（PPH ₃）₂ CL]得到[（η ⁵ -C ₅ H ^ ₅）的RuCl { Ô -Ph ₂ P（C ₆ H ^ ₄）{1,2,3-N ₃ C（PH）C（PPH ₂）}} - κ ² -P，P]（8），而用[（η茹的相似反应⁶ - p -cymene）氯₂ ] ₂以2：1的摩尔比产生阳离子络合物[（η ⁶ - p-cymene）的RuCl { Ô -Ph ₂ P（C ₆ H ^ ₄）{1,2,3-N ₃ C（PH）C（PPH ₂）}} - κ ² -P，N]氯（9）。类似地，治疗的2与[M（COD）（Cl）的₂ ]（M = Pd和Pt）以1：1的摩尔比，得到的Pd ^II和Pt ^II络合物[{ ö -Ph ₂ P（C ₆ H ^ ₄） {1,2,3-N ₃ C（PH）C（PPH ₂）} - κ ² -P，P}的PdCl ₂ ]（10）和[{ ö -Ph ₂P（C ₆ H ^ ₄）{1,2,3-N ₃ C（PH）C（PPH ₂）} - κ ² -P，P}氯铂酸₂ ]（11）。2与2当量的反应。[AuCl（SMe ₂）]的合成得到[Au ₂ Cl ₂ { o -Ph ₂ P（C ₆ H ₄）{1,2,3-N ₃ C（Ph）C（PPh ₂）}}-μ-P ，P]（12）。大多数复合物已在结构上进行了表征。钯配合物10对无铜的Sonogashira炔基化/环化反应显示出优异的催化活性。

更新日期：2018-07-18

点击分享查看原文

点击收藏

公开下载

阅读更多本刊最新论文本刊介绍/投稿指南11