کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
1325865 | 1499944 | 2010 | 10 صفحه PDF | دانلود رایگان |
The reaction of Ph2PCH2PPh2 (dppm) with BrCH2C(O)C6H4NO2 in chloroform produces the new phosphonium salt [Ph2PCH2PPh2CH2C(O)C6H4NO2]Br (1). Further, by reacting the phosphonium salt with appropriate base the bidentate phosphorus ylide, Ph2PCH2PPh2C(H)C(O)C6H4NO2 (2) was obtained. The reaction of ligand 2 with mercury(II) halides in dry methanol led to the formation of the P, C-coordinated mononuclear complexes [HgX2(Ph2PCH2PPh2C(H)C(O)C6H4NO2)] [X = Cl (3), Br (4), I (5)]. Characterization of the obtained compounds was performed by elemental analysis, IR, 1H, 31P, and 13C NMR. The X-ray crystal structure of 5 as well as the complex derived from crystallization of 4 in DMSO, [HgBr2(Ph2PCH2PPh2C(H)C(O)C6H4NO2)(DMSO)] (6), is reported. In both complexes 5 and 6 the title ylide is coordinated through the ylidic carbon and the phosphine atom. However, in compound 6 the Hg–C bond length is considerably weakened due to coordination of DMSO molecule to the metal ion and locating of ylidic carbon atom in the axial position of the resulting trigonal bipyramidal complex. Theoretical studies on ligand and all complexes at DFT (B3LYP) level of theory are also reported. The results show that the addition of DMSO molecule to the compound 4 and formation of compound 6 is energetically favored.
The reaction of mercury(II) halides with a new bidentate phosphorus ylide in 1:1 molar ratio yielded P, C-coordinated mononuclear complexes. The reaction of [HgBr2(Ph2PCH2PPh2C(H)C(O)C6H4NO2)] (4) by DMSO obtains complex [HgBr2(Ph2PCH2PPh2C(H)C(O)C6H4NO2)DMSO] (6) containing coordinated DMSO molecule, and formation of a pseudo five-coordinated Hg(II) complex.Figure optionsDownload as PowerPoint slide
Journal: Journal of Organometallic Chemistry - Volume 695, Issues 10–11, 15 May 2010, Pages 1441–1450