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

作　　者：Lewandowski, W.(Institute of General Chemistry. warsaw Agricultural University.SGGW. 02-528 Warsaw, Rakowiecka 26/30, Poland)(Matrix isolation IR spectra were obtained during author’s stay at the Marquette University, Milwaukee, WI 53233(USA). 

出　　处：《无机化学学报》1994年第1期6-12,共7页Chinese Journal of Inorganic Chemistry

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）．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 andP=10-5-10-5- 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] and1090cm-1 [Os(TPP)O2] that decompose at 240-270K the bridging dimer structure. Substitution of OEP byTPP in adducts causes more considerable changes in v(O2) band frequencies in case of Ru, as comparedwith Fe and Co.

关 键 词：八乙基卟啉 四苯基卟啉 钌 络合物 

分 类 号：O614.821[理学—无机化学]