Syntheses, Solid-State Structures, and Solution Studies by VT 31P NMR of [Zn{Se2P(OEt)2}2](infinity) and [Zn2{Se2P(OiPr)2}4]

Complexes [Zn{Se2P(OEt)2}2](infinity) (1) and [Zn2{Se2P(OiPr)2}4] (2) are prepared from the reaction of Zn(ClO4)2·6H2O and (NH4) [Se2P(OR)2] (R = Et and iPr) in a molar ratio of 1:2 in deoxygenated water at room temperature. Positive FAB mass spectra show m/z peaks at 968.8 (Zn2L3+) and 344.8 (ZnL+) for 1 and m/z at 1052.8 (Zn2L3+) for 2. 1H NMR spectra exhibit chemical shifts at 1.43 and 4.23 ppm for 1 and 1.41 and 4.87 ppm for 2 due to Et and iPr group of dsep ligands. While the solid-state structure of compound 1 is a one-dimensional polymer via symmetrically bridging dsep ligands, complex 2 in the crystalline state exists as a dimer. In both 1 and 2, zinc atoms are connected by two bridging dsep ligands with an additional chelating ligand at each zinc atom. The dsep ligands exhibit bimetallic biconnective ((mu)2, (eta)^2) and monometallic biconnective ((eta)^2) coordination patterns. Thus, each zinc atom is coordinated by four selenium atoms from two bridging and one chelating dsep ligands and the geometry around zinc is distorted tetrahedral. The Zn-Se distances range between 2.422 and 2.524 (angstrom). From variable-temperature 31P NMR studies it has been found that monomer and dimer of the complex are in equilibrium in solution via exchange of bridging and chelating ligands. However, at temperature above 40 °C the complex exists as a monomer and shows a very sharp peak while with lowering of the temperature the percentage of dimer increases gradually at the expense of monomer. Below -90 °C the complex exists as a dimer and two peaks are observed with equal intensities which are due to bridging and chelating ligands. 77Se NMR spectra of both complexes at -30 °C exhibit three doublets due to the presence of monomer and dimer in solution.