European Journal of Inorganic Chemistry p. 4992 - 5004 (2010)
Update date:2022-08-30
Topics:
Casas, Jose S.
Casanova, Noelia
Garcia-Tasende, Maria S.
Sanchez, Agustin
Sordo, Jose
Touceda, Angeles
Vazquez, Saulo
The syntheses and characterizations of the new heteroleptic complexes [PbPh2(OAc)(N2-L1)]?MeOH?EtOH, [PbPh2(OAc)(N3-L2)]?H2O, [Pb(OAc)(N2-L1)], [Pb(OAc)(N3-L 1)]?3H2O and [Pb(OAc)(N2-L2)] {HL1 = isatin-3-thiosemicarbazone, HL2 = isatin-3-(N 1-methylthiosemicarbazone); N2-Lx = thiosemicarbazonate bound through O,S and the hydrazinic [N(2)] nitrogen atom; N3-Lx = thiosemicarbazonate bound through the O,S and the iminic [N(3)] nitrogen atom} are described. The single-crystal X-ray structures of HL2, [PbPh2(OAc)(N2-L1)] ?MeOH?EtOH, [PbPh2(OAc)(N3-L2)] ?H2O, [Pb(OAc)(N2-L1)] and [Pb(OAc)(N 3-L1)]?3H2O have been solved. The organometallic compounds [PbPh2(OAc)(N2-L 1)]?MeOH?EtOH and [PbPh2(OAc)(N 3-L2)]?H2O have a roughly similar distorted bipyramidal pentagonal stereochemistry, with apical phenyl groups and both the O,Nx,S-coordinated Lx- and the anisobidentate AcO- ligands in the equatorial plane. In [PbPh2(OAc) (N2-L1)]?MeOH?EtOH, the (N2-L 1)- ligand forms a four- and a six-membered chelate ring with the metal, whereas in PbPh2(OAc)(N3-L 2)]?H2O the two chelate rings formed by (N 3-L2)- are five-membered. The PbII complexes, [Pb(OAc)(N2-L1)] and [Pb(OAc)(N 3-L1)], which were isolated from the same solution, are linkage isomers. These compounds have a rather irregular stereochemistry that suggests the presence of a stereochemically active lone electron pair; in [Pb(OAc)(N2-L1)] the (L1)- ligand is O,N2,S-coordinated and in [Pb(OAc)(N3-L1)] this ligand is O,N3,S-coordinated. Analyses of all these systems in solution by 1H and 13C NMR spectroscopy showed that during synthesis the kinetically controlled O,N2,S isomer formed first due to the rigidity of the ligand. If the compound remains in solution, slow partial evolution to the O,N3,S isomer occurs. DFT calculations predict that [Pb(OAc)(N3-L1)] is slightly more stable than [Pb(OAc)(N2-L1)] both in the gas phase and in DMSO solution. The calculations also modelled structures for the two isomers close to those obtained by X-ray diffraction studies. Solid state and solution studies indicated that, in the title derivatives, the thiosemicarbazone chain is initially bound by N2,S coordination, but evolves with time to form the N3,S-linkage isomer.
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