60 Synthesis and Structural Characterization of Asymmetric OPNPO and SPNPS Type Ligands and Their in(III), Sb(III), Bi(III), Sn(II) and Cd(II) Metal-Organic Complexes

Wednesday, November 4, 2009
Ballroom A+B (Camino Real Hotel)
Marcela Lopez , Centro de Investigaciones Quimicas, Universidad Autonoma del Estado de Morelos, Cuernavaca, Mexico
Diana Vargas , Centro de Investigaciones Quimicas, Universidad Autonoma del Estado de Morelos, Cuernavaca, Mexico
Raymundo Cea , Instituto de Quimica, Universidad Nacional Autonoma de Mexico, Mexico DF, Mexico
Reaction of Ph2P(X)NH2 with 2-chloro-2-oxa(thia)-5,5-diethyl-1,3,2-dioxaphosphorinanes yields two novel imidodiphosphinic acids of the composition (OPR2)NH(OPR") 1 and (SPR2)NH(SPR") 2 with R=Ph; R”= -OCH2CEt2CH2O-. The crystal and molecular structures of 1 and 2 were determined by X-ray diffraction analysis, showing that both compounds reveal P=X---H-N intermolecular interactions forming supramolecular polymeric chains in the first case and dimers in the second case. The P=O and P=S groups in 1 and 2 have transoid orientation with (O)SP∙∙∙PS(O) torsion angles of 174.6/179.5 and 166.3° for 1 and  2, respectively. The ML2 and ML3 metal-organic complexes In[(OPR2)NH(OPR")]3 1a, Sb[(OPR2)NH(OPR")]3 1b, Bi[(OPR2)NH(OPR")]3 1c, In[(SPR2)NH(SPR")]3 2a, Cd[(SPR2)NH(SPR")]2 2b and Bi[(SPR2)NH(SPR")]3 2c were prepared by reacting the corresponding metal(II,III) chlorides with  the potassium salts of the imidodiphosphinic acids. These complexes were characterized by IR, 1H, 13C and 31P NMR spectroscopy. For 1a, 2a and 2b the crystal and molecular structures could be determined by X-ray diffraction analysis. The imidodiphosphinate ligands act as monometallic biconnective units in all complexes. The structural arrangements around the metal center in compounds 1a and 2a are distorted octahedral and complex 2b is tetrahedral. The six-membered inorganic MO(S)2P2N and the 1,3,2-dioxaphosphorinane rings have distorted chair conformations.
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