The synthesis and characterization of potassium 2,2-bipyridinetetranitroruthenate

被引:14
作者
Freedman, DA
Janzen, DE
Mann, KR [1 ]
机构
[1] SUNY Coll New Paltz, Dept Chem, New Paltz, NY 12561 USA
[2] Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA
关键词
D O I
10.1021/ic010548m
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
We report a convenient synthesis of K-2[Ru(bpy)(NO2)(4)] via the thermal displacement of benzene from, [(Bz)Ru(bpy)Cl]Cl (Bz =eta (6)-C6H6; bpy = 2,2'-bipyridine) by nitrite ion in methanol, solution. K-2[Ru(bpy)(NO2)(4)] has been fully characterized by elemental analysis, X-ray crystallography, and H-1 NMR, IR, UV-vis, and emission spectroscopy. Reaction of K-2[Ru(bpy)(NO2)(4)] with pyridine under mild or forcing conditions produces fac-K[Ru(bpy)(NO2)(3)(py)] and cis-[Ru(NO2)(2)(bpy)(PY)(2)] (py = pyridine), respectively. We report full characterization data for these compounds, including crystal structures. The d pi (Ru) --> pi*(bpy) charge-transfer band in the electronic spectra of K-2[Ru(bpy)(NO2)(4)] and fac-[Ru(bpy)(NO2)(3)(py)] displays a significant solvent dependence. The energy of the absorption band correlates linearly with the Gutmann solvent acceptor number. The solvatochromic response of these nitro complexes is essentially identical to that of the analogous cyanide complexes, indicating that the mechanism previously proposed to explain the solvatochromism of the cyanide complexes may need to be reexamined.
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页码:6009 / 6016
页数:8
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