Novel structural variation of silver(I)-pyridine complexes in nitromethane as studied by X-ray absorption spectroscopy |
| |
Authors: | Misaki Katayama Eri Kato Shigenobu Funahashi |
| |
Affiliation: | a Department of Applied Chemistry, Ritsumeikan University, Kusatsu 525-8577, Japan b Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan |
| |
Abstract: | The XAFS spectra were measured at around the Ag K-edge of the Ag(I) ion in nitromethane (NM) with a variety of concentrations of pyridine (PY). In NM without PY, the Ag(I) ion is tetrahedrally solvated by four NM molecules similar to those in most solvents. The Ag-O bond length in NM solvent is longer than that in aqueous solution, indicating the low donating ability of NM. The mono-, bis-, tris-, and tetrakis-pyridine complexes are formed in NM by the addition of PY. The EXAFS analyses reveal that the structure of the formed PY complex in NM is linear for Ag(py)(nm)+, linear for , triangular for , and tetrahedral for . The longer Ag-O bond length for Ag(py)(nm)+ than that for and the release of bound NM molecules at the formation of Ag(py)(nm)+ are interpreted to be due to the strong σ donating property of PY. The Ag-N bond length (220 pm) for is intermediate between 216 pm for and 228 pm for . The formation equilibria of and are analyzed on the basis of the changeover of EXAFS spectra as a function of the total concentrations of Ag+ and PY in NM. |
| |
Keywords: | XAFS Ag K edge Nitromethane Structural changeover Ag(I) complex |
本文献已被 ScienceDirect 等数据库收录! |
|