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Mercury(II) complexes of new bidentate phosphorus ylides: synthesis, spectra and crystal structures

, , , , and . CHEMICAL PAPERS, 68 (5): 624-632 (May 2014)
DOI: {10.2478/s11696-013-0487-5}

Abstract

The reaction of dppm (1,1-bis(diphenylphosphino)methane) with 2-bromo-4-phenylacetophenone and benzyl bromoacetate in chloroform produces new phosphonium salts, Ph2PCH2PPh2CH2C(O) C6H4PhBr (I) and Ph2PCH2PPh2CH2COOCH2PhBr (II). By allowing the phosphonium salts to react with the appropriate base, the bidentate phosphorus ylides, Ph2PCH2PPh2=C(H)C(O)C6H4Ph (III) and Ph2PCH2PPh2=C(H)C(O)OCH2Ph (IV), were obtained. The reaction of these ligands with mercury(II) halides in dry methanol led to the formation of the mononuclear complexes \HgX2(Ph2PCH2PPh2C(H)C(O)C6H4Ph)\ (X = Cl (V); X = Br (VI); X = I (VII)) and \HgX2(Ph2PCH2PPh2C(H)COOCH2Ph)\ (X = Cl (VIII); X = Br (IX); X = I (X)). The FTIR and H-1, P-31 and C-13 NMR spectra were studied. The structure of compound III was unequivocally determined by the single-crystal X-ray diffraction technique. Single-crystal X-ray analysis of the \HgBr2(Ph2PCH2PPh2C(H)C(O)C6H4Me)\ complex (XI) revealed the presence of a mononuclear complex containing the Hg atom in a distorted tetrahedral environment. In all complexes, the ylides referred to above were coordinated through the ylidic carbon and the phosphine atom. (C) 2013 Institute of Chemistry, Slovak Academy of Sciences

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