Complex Formation of [Ph2P(O)I2 C=CH2 and [Ph2 P(O) I2 C=PPh3 with Phosphorus and Tantalum Pentafluorides |
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| Authors: | E G Ilyin M V Simonov V Kovalev I V Leontieva I M Aladzheva T A Mastryukova |
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| Institution: | 1. N.S. Kurnakov Institute of General and Inorganic Chemistry, Academy of Sciences of the USSR , Leninskii prosp. 31, Moscow , 117907 , USSR;2. A.N. Nesmeyanov Institute of Organo-Element Compounds, Academy of Sciences of the USSR , Vavilov Str. 28, Moscow , 117334 , USSR |
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| Abstract: | Abstract Reactions of PF5 and TaF5 with Ph2P(O)]2 C=CH2 (I) and Ph2P(O)]2 C=PPh3 (II) in MeCN and CH2Cl2 were studied by means of 19F, 31P, 1H and 13C NMR spectroscopy. It has become evident, that one or two phosphoryl groups in (I) and (II), as well as in cis- and trans-Ph2P(O)CH=CHP(O)Ph2, are involved in complex formation. The formation of tetra-fluoro cations PFL and PF4L along with pentafluorocom-plexes PF5L and TaF5L was found. Ligands are coordinated with central ions of complexes as chelates. The trans-atoms F1 of TaF 5L are nonequivalent because of nonsymmetric position to the Ph3P-group. The F1-atoms in PF4L are supposed to be symmetric to the Ph3P-group. The formation of tri-fluorocomplexes TaOF3L was also observed. Since the position of 19F NMR resonance lines of TaOF3L is near to that of pentafluorocomplexes, it can be supposed that either the change of Ta coordination number takes place, either oxygen atom comes into complex with inner sphere in the reaction with ligand or during hydrolysis. |
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