双脂肪胺钌卟啉的合成,结构表征和晶体结构.doc

双脂肪胺钌卟啉的合成,结构表征和晶体结构 第2期 l997年6月 ④\} 无机化学 JOURNAL0FIN0RGANICCHEMISTRY v0I.j3.K..2 2une.1997 双脂肪胺钌Ⅱ卜啉的合成,结构表征和晶体结构 李早荚 (武汉大学化学系,武汉430072) 支志明 (香港大学化学系,香港) 恨 车文讨论了一系列双脂肪胺钉卟啉配合物,包括Ru()(Por)(HNR):和Ru(,,)(Por)(HNR): ~Por=四苯基卟啉(TPP),中位一四(对甲苯基)卟啉(TTP),中位四(对氯苯基)卟啉(|cI—TPP);R= 敦丁基,异丙基,环己基,正辛基,正十二烷基,RJ一甲基和乙基]的合成.结构表征和晶体结构测定 钉羰基叶啉与间一氯过苯甲酸的反应混合物用过量的脂肪胺处理,得到高收率的积脂肪胺钉卟啉配 合物.所有的新配合物经棱磁共振光谱,红外光谱,紫外光谱以及元素分析得到证实其中,配合物 Ru()(Pot)(H-NBtl—t):的结构已由x一射线晶体结构测定.在Ru()(Pot)(H}NBu—t)}分子中, Ru—N(Pot)和Ru-N(H:NBu—t)键长分别为2.04l^和2.j75A. 西己合物 关键词: .!堕旦噬合成结构表征墨结构测定 BIS(ALIPHATICAMINE)RUTHENIUM(i)PORPHYRINSSYNTHESIS. SPECTROSCOPYANDCRYSTALSTRUCTURE LiZaoying {DepartmentofChemistry,WuhanUniversity,Wuhan430072) CheChiming (DepartmentofChem~try,TheUniversityofHongKong,HongKong) Thesynthe~stcharacterizationandreactivitiesofaseriesofrutheniumporphyrinsin— eludingRu(Por)(H2NR)2andRu(Por)(HNR2)2[Por—tetraphenylporphyrinato (TPP),rcte~otetrakis(p—toIyI)porphyrina协(TTP),搬瑚一tetrakis(4一chloropheny1)porphyri— nato(4-C1一TPP);R=tert-butyl,isopropyl,cyclohexyl,—oetyl,—dodecyl,R=methyl, ethylaredescribed.ThereactionofRu(Pot)(Co)(MeOH)withm—chloroperoxylbenzoic acid(m-CPBA)followedbytreatmentofthereactionmixturewithexce璐aliphaticamines readilygavebis(aliphaticamine)ruthenium(Ⅱ)porphyrinsinhighyields.Allthenew complexeshavebeencharacter.2cdbyHNMR.{R.andUV—Vislblespectroscopy.ThcX— raycrystalstructureofRu(TTP)(H2NBu)2hasbeendetermined.TheRu—N(Por)andRu一 iveflt199:.:1996…5l LiZaoyins?female?inJuly1949?ar~cviatepTof啪.eut~fltresearc~|nr【islnthestudyonsynthesr~andpr~crtlcsof macroc~,elicpolyamin~andmetalcom0l~~- ?l36?无机化学第l3卷 N(H2NBu)distancesinRu(1vrP)(H2NBu)2are0.204lnmand0.2175nm,respective— . , Kevw0rds 0Introduction alhati~aminerutheniumpotphyrtnsynthesischarach~rizeation crystalstructuredetcxmlnation Althoughthechemistryoftransitionmetalaminecomplexeshasbeenintensivelystudied,reia一 tivelyfewreportshavebeenmadeonthebis(amine)adductsofmetalloporphyrins,andsuchreports havemainlyconcentratedonaromaticaminesaxialfig,ands.suc