کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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1311591 | 975334 | 2008 | 7 صفحه PDF | دانلود رایگان |
![عکس صفحه اول مقاله: Synthesis and coordination of the bifunctionalized ylides Ph2P(CH2)n(Ph)2PCHCOOMe (n = 1, 2) and ketenylidene Ph2P(CH2)2(Ph)2PCCO to Pd and Pt complexes Synthesis and coordination of the bifunctionalized ylides Ph2P(CH2)n(Ph)2PCHCOOMe (n = 1, 2) and ketenylidene Ph2P(CH2)2(Ph)2PCCO to Pd and Pt complexes](/preview/png/1311591.png)
In this paper it is reported the synthesis of the phosphonium salts [Ph2P(CH2)n(Ph)2PCH2COOMe]Br (n = 1 (1), 2 (2)) and [Ph2P(CH2COOMe)(CH2)n(Ph)2PCH2COOMe]Br2 (n = 3 (3)) derived from the reactions of the diphosphines dppm, dppe and dppp with methyl bromoacetate. By reaction of the monophosphonium salt of dppm and dppe with the strong base Na[N(SiMe3)2] the corresponding carbonyl stabilized ylides Ph2P(CH2)n(Ph)2PCHCOOMe (n = 1 (4), 2 (5)) were obtained. The Ph2P(CH2)2(Ph)2PCHCOOMe (5) ylide was reacted with Pd(II) and Pt(II) substrates. From these reactions were isolated exclusively complexes in which the ylide was chelated to the metal through the free phosphine group and the ylidic carbon atom. A further reaction of the Ph2P(CH2)2(Ph)2PCHCOOMe (5) ylide with 1.5 equiv. of Na[N(SiMe3)2] gives the bifunctionalized ketenylidene Ph2P(CH2)2(Ph)2PCCO (6) system. This cumulenic ylide reacts with Pt(II) complexes to form a chelated derivative in which IR and NMR spectra suggest the breaking of the CC bond of the –CCO group.
The synthesis of the ylides Ph2P(CH2)n(Ph)2PCHCOOMe (n = 1 (1), 2 (2)), the ketenylidene Ph2P(CH2)2(Ph)2PCCO (6) and their coordination to Pd(II) and Pt(II) transition metal complexes are reported. Both ylides chelate to the metal centre through the free phosphine group and the ylidic carbon atom. The ketenylidene coordinates breaking the CC bond of the –CCO moiety.Figure optionsDownload as PowerPoint slide
Journal: Inorganica Chimica Acta - Volume 361, Issue 11, 27 July 2008, Pages 3177–3183