PREPARATION AND PROPERTIES OF INCLUSION-COMPOUNDS OF TRANSITION-METAL COMPLEXES OF CYCLOOCTA-1,5-DIENE AND NORBORNADIENE WITH CYCLODEXTRINS
PREPARATION AND PROPERTIES OF INCLUSION-COMPOUNDS OF TRANSITION-METAL COMPLEXES OF CYCLOOCTA-1,5-DIENE AND NORBORNADIENE WITH CYCLODEXTRINS
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DOI：
10.1021/om00113a007
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发表时间：
1989-11-01
期刊：
影响因子：
2.8
通讯作者：
TAKAHASHI, S
中科院分区：
文献类型：
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作者：
HARADA, A;YAMAMOTO, S;TAKAHASHI, S
制备了环八烷二烯(COD)、降冰片二烯(NBD)与环糊精的Rg、Pd包合物。3-环糊精(/3-CD)与双(74-环辛基-L，5-二烯)联二氢呋喃、[Rh(GX)(CODd)]2(X=Cl，Br，I)和双(/^-氯)双(？4-降冰片二烯)镝[Rh(#i-CI)(NBD)]2在结晶态高产率地合成了二对一(环糊精对客体)包合物。3-环糊精与环辛二烯-1，5-二烯-二卤化铂X_2(X=氯、溴、碘)反应高产率地得到一对一包合物，而-环糊精与铂(COD)_2形成1：1包合物，而不与铂(COD)_Cl2形成包合物。-环糊精不与环辛二烯和降溴二烯形成任何过渡金属络合物。包合物是热稳定的，在真空中加热到200℃时不释放客体，在此温度下非包合物[Rh(/u-Cl)(COD)]2已经分解。用核磁共振、红外光谱、紫外光谱和圆二色谱对包合物进行了表征。/3-Cd-[Rh(/u-Cl)(COD)]2存在较大的诱导棉花效应。在/3-Cd存在下，[Rh(/？-Cl)(COD)]2的核磁共振谱显示了两组不同Cd物种的共振，分别归属于游离Cd和络合Cd。将讨论绑定模式。
Inclusion compounds of rhodium and platinum complexes of cycloocta-1, 5-diene (COD) and norbomadiene (NBD) with cyclodextrins were prepared. Two-to-one (cyclodextrin to guest) inclusion compounds were obtained in high yields in a crystalline state by the treatment of/3-cyclodextrin (/3-CD) with bis (¿¿-halo) bis (? 74-cycloocta-l, 5-diene) dirhodium,[Rh (gX)(COD)] 2 (X= Cl, Br, I), and bis (/^-chloro) bis (?? 4-norbornadiene) dirhodium,[Rh (# i-C1)(NBD)] 2. The formation of inclusion compounds is selective. One-to-one inclusion compounds were obtained by the reaction of/3-CD with (cycloocta-1, 5-diene) platinum dihalides, Pt (COD) X2 (X= Cl, Br, I), in high yields, while-CD formed 1: 1 inclusion compounds with Pt (COD) I2 but not with Pt (COD) Cl2.-Cyclodextrin did not form inclusion compounds with any transition-metal complexes of cyclooctadiene and norbomadiene. The inclusion compounds are thermally stable and do not liberate the guest when heated to 200 C in vacuo at which temperature the nonincluded guest [Rh (/u-Cl)(COD)] 2 already decomposed. The inclusion compounds were characterized by NMR, IR, UV, and circular dichroism spectra. A large induced Cotton effect was observed with/3-CD-[Rh (/u-Cl)(COD)] 2. The NMR spectrum of [Rh (/¿-Cl)(COD)] 2 in the presence of/3-CD shows two sets of resonances for two different CD species that are assigned to free/3-CD and the complexed/3-CD, respectively. The binding mode will be discussed.