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.
出处
《无机化学学报》
SCIE
CAS
CSCD
北大核心
1994年第1期6-12,共7页
Chinese Journal of Inorganic Chemistry
关键词
八乙基卟啉
四苯基卟啉
钌
络合物
dioxygen of Ru(Ⅱ) and Os(Ⅱ) porphyrin matrix isolation IR spectroscopy
