Inorganic Chemistry, Vol.33, No.19, 4226-4230, 1994
Lead(II) Complexes Containing 2 Different Polydentate Ligands - Crystal and Molecular-Structure of (HB(3,5-Me(2)Pz)(3))Pb(3,5-Me(2)Pzh)(3)Cl (Pz=pyrazolyl Ring), a Cationic-Anionic, Double-Coordination Complex
The reaction in water of PbCl2 with equimolar amounts of both Na((C5H5)Co[P(O)(OC2H5)(2)](3)} and K[HB(pz)(3)] (pz = pyrazolyl ring) yields {(C5H5)Co[P(O)(OC2H5)(2)](3)}Pb[HB(pz)(3)]. A similar reaction with SnCl2 in CH2Cl2 yields {(C5H5)Co[P(O)(OC2H5)(2)](3)}Sn[HB(pz)(3)]. The reaction of {(C5H5)Co[P(O)(OC2H5)(2)](3)}Pb-2 and [H2B(pz)(2)]Pb-2 yields {(C5H5)Co[P(O)(OC2H5)(2)](3))Pb[H2B(pz)(2)]. The Pb-207 NMR resonances for the mixed-ligand lead complexes are located fairly close to the average of the two respective symmetrical (ligand)(2)Pb complexes. {[HB(3,5-Me(2)pz)(3)]Pb(3,5-Me(2)pzH)(2)}NO3 is isolated from the reaction of Pb(NO3)(2), P(O)(3,5-Me(2)pz)(3), and K[HB(3,5-Me(2)pz)(3)]. In a similar reaction mixture, containing small amounts of HCl, [HB(3,5-Me(2)pz)(3)]Pb(3,5-Me(2)pzH)(3)Cl forms, as characterized by X-ray crystallography. The structure contains a six-coordinate lead(II) cation in a capped octahedral geometry, with the lone pair on the lead atom in the capping position of the face formed by the three 3,5-Me(2)pzH ligands and a chloride anion hydrogen bonded to the N-H groups of these 3,5-Me(2)pzH ligands. The reaction of 1 equiv of [HB(3,5-Me(2)pz)(3)](-) and Pb(NO3)2 leads to the formation of [HB(3,5-Me(2)pz)(3)]Pb(eta(1)-NO3), characterized in the solid state by X-ray crystallography. The [HB(3,5-Me(2)pz)(3)](-) ligand is tridentate and the nitrate ligand monodentate, leading to a structure best described as pseudo trigonal bipyramidal with the oxygen atom in an axial site and the stereoactive lone pair in an equatorial site. The reaction of [HB(3,5-Me(2)pz)(3)]Pb(eta(1)-NO3) and [H2B(pz)(2)](-) yields [HB(3,5-Me(2)pz)(3)]Pb[H2B(pz)(2)], assigned as a five coordinate complex from Pb-207 NMR. Crystal data : [HB(3,5-Me(2)pz)(3)]Pb(NO3), monoclinic, P2(1)/c, a = 14.218(3) (3) Angstrom, b = 7.842(2) Angstrom, c = 18.319(6) Angstrom, beta = 94.36(2)degrees, V = 2037 Angstrom(3), Z = 4, R = 4.7%; [Hb(3,5-Me(2)pz)(3)]Pb(3,5-Me(2)pzH)(3)Cl, trigonal, P31c, a = 11.069(2) Angstrom, c = 17.319(3) Angstrom, V = 1838 Angstrom(3), Z = 2, R = 2.51%.