| 八乙墓卟啉和四苯基卟啉合钌(Ⅱ)及锇(Ⅱ)的二氧加合物的红外光谱 |
| INFRARED SPECTRA OF DIOXYGEN ADDUCTS OF RUTHENIUM(Ⅱ) AND OSMIUM(Ⅱ) OCTAETHYLPORPHINE AND TETRAPHENYLPORPHINE |
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| 摘要: OEP(八乙基卟啉阴离子)和TPP(四苯基卟啉阴离子)合钌(Ⅱ)和锇(Ⅱ)的二氧加合物由matrix分离技术得到(T=20-43K,P=10-5-10-6torr).为了确定v(O2)带的归属应用了同位素取代法16O2/18O2.IR谱说明对于钌的两种加合物(指OEP和TPP)都有两种异构体,其V(16O2)频率为:Ru(OEP)O2,1141和1103cm-1;Ru(TPP)O2,1167和1114cm-1.Os(TPP)O2只生成一种异构体,v(16O2)=1090cm-1,异构体v(16O2):[Ru(OEP)O2],1141cm-1,[Ru(TPP)O2],1167cm-1,这些加合物约在100K时分解,它们的结构指定为endon,而异构体[Ru(OEP)O2],1103cm-1,[Ru(TPP)O2],1114cm-1和[Os(TPP)O2],1090cm-1,在240-270K分解,它们的结构指定为桥联二聚体。在加合物中,将OEP换成TPP引起的钌加合物v(O2)频率的改变比铁和钴加合物更大。v(O2)相对强度的变化顺序为:Fe(Ⅱ)→Ru(Ⅱ)→Os(Ⅱ). |
| 关键词: 卟啉钌(Ⅱ)和锇(Ⅱ)配合物的二氧化物 matrix分离技术 红外光谱 |
| 基金项目: |
| Abstract: Dioxygen adducts of Ru(Ⅱ) and Os(Ⅱ) with OEP (octaethylporphyrinato anion) and TPP(tetraphenylporphyrinato anion) were obtained by using the matrix isolation technique (T=20-43K and P=10-5-10-6 torr). To assign v(O2) bands the isotope substitution 16O2/ 18O2 has been applied. IRspectroscopy revealed that in the case of Ru adducts two isomers exist in both adducts for which v(16O2)band frequencics amount to 1141 and 1103cm-1 for Ru(OEP)O2; for Ru(TPP)O2 they are 1167 and11 14cm-1. Os(TPP)O2 forms one isomer only for which (16O2) = 1090cm-1. Isomers of v(16O2) frequencies:1141cm-1 [Ru(OEP)O2] and 1167cm-1 [Ru(TPP)O2] which decompose at ca 100K have been assigned theend-on structure, while isomers 1103cm-1 [Ru(OEP)O2], 1114cm-1 [Ru(TPP)O2] and 1090cm-1 [Os(TPP)O2] that decompose at 240-270K the bridging dimer structure. Substitution of OEP by TPP in adducts causes more considerable changes in v(O2) band frequencies in case of Ru, as comparedwith Fe and Co. |
| Keywords: dioxygen of Ru(Ⅱ) and Os(Ⅱ) porphyrin matrix isolation IR spectroscopy |
| 投稿时间：1992-10-09 |
| 摘要点击次数: 1046 |
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| Lewandowski. W..八乙墓卟啉和四苯基卟啉合钌(Ⅱ)及锇(Ⅱ)的二氧加合物的红外光谱[J].无机化学学报,1994,10(1):6-12. |
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