山西大学学报（自然科学版）
山西大學學報（自然科學版）
산서대학학보（자연과학판）
JOURNAL OF SHANXI UNIVERSITY
2009年
3期
436-442
,共7页
铊(Ⅲ)%邻啡咯啉(Phen)%氮给体配体%~(205)Tl%NMR谱
鉈(Ⅲ)%鄰啡咯啉(Phen)%氮給體配體%~(205)Tl%NMR譜
사(Ⅲ)%린배각람(Phen)%담급체배체%~(205)Tl%NMR보
Thallium(III)%Phenanthroline(phen)%N-donor ligands%NMR spectroscopy
合成了新的三价金属铊与配体邻啡咯啉(Phen)和8-羟基喹啉(Oxine)的络合物,并应用多核核磁共振(~1H,~(13)C和~(205)Tl)渡谱和振动光谱,系统地对所合成的络合物进行了溶液和固相的表征.~(205)Tl核磁共振波谱表明,单配体络合物[Tl(phen)]~(3+),双配体络合物[Tl(phen)_2]~(3+)和三配体络合物[Tl(phen)_3]~(3+)以化学平衡的形式存在于二甲基砜(DMSO)和乙腈(CH_3CN)溶液中.并在DMSO溶液中,测定了三配体络舍物[Tl(phen)_3](ClO_4)_3 (1)和四配体络舍物[Tl(oxine)_4] (ClO_4)_3(2)的~1H和~(13)C NMR谱,其自旋-自旋耦合常数(Tl(I=1/2)-~(13)C和Tl(I=1/2)-~1H)均被观测到.从二维共振谱(~(13)C-~1H COSY图谱),四配体络合物[Tl(oxine)_4]~(3+)中C-H联结和其复杂的自旋-自旋耦合~1H NMR图谱均被明确地归属和指认.紫外-可见光谱表明配体到金属的电荷转移吸收谱(LMCT)分别为315 nm(ε=1.65×10~3mol~(-1)·cm~(-1))(1)和375 nm(ε=7.48×10~3mol~(-1)·cm(-1))(2).由此可见,三价铊与配体邻啡咯啉(Phen)和8-羟基喹啉(Oxine)均都生成了稳定的络合物.
閤成瞭新的三價金屬鉈與配體鄰啡咯啉(Phen)和8-羥基喹啉(Oxine)的絡閤物,併應用多覈覈磁共振(~1H,~(13)C和~(205)Tl)渡譜和振動光譜,繫統地對所閤成的絡閤物進行瞭溶液和固相的錶徵.~(205)Tl覈磁共振波譜錶明,單配體絡閤物[Tl(phen)]~(3+),雙配體絡閤物[Tl(phen)_2]~(3+)和三配體絡閤物[Tl(phen)_3]~(3+)以化學平衡的形式存在于二甲基砜(DMSO)和乙腈(CH_3CN)溶液中.併在DMSO溶液中,測定瞭三配體絡捨物[Tl(phen)_3](ClO_4)_3 (1)和四配體絡捨物[Tl(oxine)_4] (ClO_4)_3(2)的~1H和~(13)C NMR譜,其自鏇-自鏇耦閤常數(Tl(I=1/2)-~(13)C和Tl(I=1/2)-~1H)均被觀測到.從二維共振譜(~(13)C-~1H COSY圖譜),四配體絡閤物[Tl(oxine)_4]~(3+)中C-H聯結和其複雜的自鏇-自鏇耦閤~1H NMR圖譜均被明確地歸屬和指認.紫外-可見光譜錶明配體到金屬的電荷轉移吸收譜(LMCT)分彆為315 nm(ε=1.65×10~3mol~(-1)·cm~(-1))(1)和375 nm(ε=7.48×10~3mol~(-1)·cm(-1))(2).由此可見,三價鉈與配體鄰啡咯啉(Phen)和8-羥基喹啉(Oxine)均都生成瞭穩定的絡閤物.
합성료신적삼개금속사여배체린배각람(Phen)화8-간기규람(Oxine)적락합물,병응용다핵핵자공진(~1H,~(13)C화~(205)Tl)도보화진동광보,계통지대소합성적락합물진행료용액화고상적표정.~(205)Tl핵자공진파보표명,단배체락합물[Tl(phen)]~(3+),쌍배체락합물[Tl(phen)_2]~(3+)화삼배체락합물[Tl(phen)_3]~(3+)이화학평형적형식존재우이갑기풍(DMSO)화을정(CH_3CN)용액중.병재DMSO용액중,측정료삼배체락사물[Tl(phen)_3](ClO_4)_3 (1)화사배체락사물[Tl(oxine)_4] (ClO_4)_3(2)적~1H화~(13)C NMR보,기자선-자선우합상수(Tl(I=1/2)-~(13)C화Tl(I=1/2)-~1H)균피관측도.종이유공진보(~(13)C-~1H COSY도보),사배체락합물[Tl(oxine)_4]~(3+)중C-H련결화기복잡적자선-자선우합~1H NMR도보균피명학지귀속화지인.자외-가견광보표명배체도금속적전하전이흡수보(LMCT)분별위315 nm(ε=1.65×10~3mol~(-1)·cm~(-1))(1)화375 nm(ε=7.48×10~3mol~(-1)·cm(-1))(2).유차가견,삼개사여배체린배각람(Phen)화8-간기규람(Oxine)균도생성료은정적락합물.
The novel complexes of monomeric thallium (III) with ligands of phenanthroline (phen) 8-hydroxyquinoline (oxine) have been synthesized and characterized by multinuclear NMR (~1H,~(13)C,~(205)Tl) spectroscopy, Raman spectroscopy. Three Tl-Phen complexes of [Tl(phen)]~(3+), [Tl(phen)_2]~(3+) and [Tl (phen)_3]~(3+) coexisted in equilibria in dimethyl sulfoxide (DMSO) and acetonitrile (CH_3CN) were proved by the ~(205)Tl NMR spectra. The ~1H and ~(13)C solution NMR spectra of [Tl(phen)_3](ClO_4)_3 (1) and [Tl (oxine)_4](ClO_4)_3(2) complexes have been measured and all the spin-spin coupling constants (Tl(I=l/2) -~(13)C and Tl(I=1/2)-~1H) have observed. Based on a COSY (~(13)C-~1H) 2D spectrum,the C-H connectivity and the complicated spin-spin coupling pattern (~1H-Tl (I=1/2)) of [Tl(oxine)_4]~(3+) cation were fully assigned. The characteristic transition absorption peaks of ligand-to-metal charge transfer (LMCT) were observed at 315 nm (1. 65×10~3 mol~(-1) · cm~(-1)) and 375 nm (7. 48×10~3 mol~(-1) · cm~(-1)) respectively for complex [Tl(Phen)_3](ClO_4)_3(1) and complex [Tl(oxine)_4](ClO_4)_3(2). In comparison,the absorption peak of complex 2 was obviously shifted to the red than that of complex 1. All the experimental results indicated that the stable thallium(III) complexes have formed with these two nitrogen and oxygen donor ligands.
