OsIII(N2)OsII complexes at the localized-to-delocalized, mixed-valence transition

被引:91
作者
Demadis, KD [1 ]
El-Samanody, ES [1 ]
Coia, GM [1 ]
Meyer, TJ [1 ]
机构
[1] Univ N Carolina, Dept Chem, Venable & Kenan Labs, Chapel Hill, NC 27599 USA
关键词
D O I
10.1021/ja982802o
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
On the basis of the appearance of v(N drop N) from 2007 to 2029 cm(-1) in CD3CN, oxidation states at Os in cis,cis-[(bpy)(2)(Cl)Os-III(N-2)Os-II(Cl)(bpy)(2)](3+) (4), trans,trans-[(tpy)(Cl)(2)Os-III(N-2)Os-II(Cl)(2)(tpy)](+) (5), [(tpm)(Cl)(2)Os-III(N-2)Os-II(Cl)(2)(tpm)](+) (7), and [(Tp)(Cl)(2)Os-III(N-2)Os-II(Cl)(2)(Tp)](-) (8) are localized. For 5 this conclusion is reinforced by the crystal structure of the BF4- salt, which shows that the Os sites are unsymmetrical. Five narrow, solvent-independent bands appear in the near-infrared. They can be assigned to a combination of intervalence (IT) and interconfigurational d pi --> d pi transitions. From integrated band intensities the magnitudes of the resonance energies from electronic coupling across the mu-N-2 bridge vary from 1500 to 2500 cm(-1) Intramolecular Os-II --> Os-III electron transfer is rapid on the time scale for solvent reorientation, but a barrier still exists from low-frequency, coupled Os-Cl and Os-N vibrations.
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页码:535 / 544
页数:10
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