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    STUDIA CHEMIA - Issue no. 4(II) / 2009  
         
  Article:   HYPERVALENT TETRA- AND TRIORGANOLEAD(IV) COMPOUNDS CONTAINING 2-(R2NCH2)C6H4 GROUPS (R = Me, Et).

Authors:  ADINA CRISTEA, ANCA SILVESTRU, CRISTIAN SILVESTRU.
 
       
         
  Abstract:  Reaction of [2-(R2NCH2)C6H4]Li with R’3PbCl or Ph2PbCl2, in 1:1 molar ratio, gave the new organolead(IV) compounds [2-(R2NCH2)C6H4]R’3Pb [R = Me, R’ = Me (1), Ph (2); R = Et, R’ = Ph (3)] and [2-(Me2NCH2)C6H4]Ph2PbCl (4). Treatment of [2-(R2NCH2)C6H4]Ph3Pb with iodine resulted in isolation of [2-(R2NCH2)C6H4]Ph2PbI [R = Me (5), Et (6)]. The iodide 5 was also obtained by halogen exchange reaction between 4 and KI. The compounds were characterized in solution by 1H and 13C NMR. The molecular structure of 2 and 4 was established by single-crystal X-ray diffraction. In both cases the nitrogen atom from the pendant Me2NCH2 arm is coordinated intramolecularly to the lead atom [Pb-N 3.051(9) Å in 2 and 2.635(8) Å in 4, respectively] leading to distorted trigonal bipyramidal geometry around the metal atom and thus to hypervalent 10-Pb-5 species. Compounds 2 and 4 crystallize as 1:1 mixtures of R- and S-isomers (planar chirality induced by the non-planar PbC3N chelate ring).

Keywords: organoleadIV) compounds, hypervalent, solution NMR studies, single-crystal X-ray diffraction
 
         
     
         
         
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