氧齿配体锝配合物 Ⅰ.氧多齿配体锝(Ⅴ)配合物的结构及其性质
-
摘要: 根据空腔模型中的经验结合规律，提出了各种含氧配位体与ＴｃＯ３＋的结合能力：ＨＯ－～ＲＯ－＞ＡｒＯ－＞Ｒ－ＰＯ３Ｈ－＞Ｒ－ＣＯ－２＞Ｃ＝Ｏ。在此序列和五配位四方锥构型基础上，解释了各氧多齿配体与ＴｃＯ３＋的结合性质。由于ＴｃＯ（ＯＨ）－４容易岐化为ＴｃＯ２·ｘＨ２Ｏ和ＴｃＯ－４，因而任何单齿氧ＴｃＯ３＋核配合物在水溶液中皆不稳定。多元醇、邻二酚、α羟基膦酸、α羟基羧酸的ＴｃＯ３＋配合物由于螯合效应，可能在水溶液中存在。Abstract: OXYGEN ATOM COORDINATED TECHNETIUM COMPLEXESⅠTHE STRUCTURE AND PROPERTIES OF TECHNETIUM (Ⅴ) COMPOUNDS WITH OXYGEN MULTIDENTATE LIGANDSLiu Guozheng Miao Zengxing Wang Yishan Fang Jidong(Isotope Department,China Institute of Atomic Energy,Beijing 102413)ABSTRACTThe sequence of binding ability of TcO3＋ core to various oxygen donor ligands is given as HO－～RO－>ArO－>RPO3H－>RCOO－>C=O based on the existing experimental data and the previously described empirical rules.The coordination characters of TcO3＋ with multidentate oxygen donor ligands are rationalized by that sequence and the square pyramidal geometry of TcO3＋ complexes.Any complex of TcO3＋ with unidentate oxygen donor ligands is unstable because of its strong trend towards disproportionation to TcO2·xH2O and TcO－4.In contrast,complexes of TcO3＋ with polyhydric alcohols,odiphenols,2hydroxy phosphonates,and 2hydroxy carboxylates may stably exist in aqueous solution due to chelating effects.Keywords Cavity model Technetium compounds Stability Oxygen coordination atom TcO3＋ core
-
-
[1] １ＳｔｅｉｇｍａｎＪ，ＥｃｋｅｌｍａｎＷＣ．ＴｈｅＣｈｅｍｉｓｔｒｙｏｆＴｅｃｈｎｅｔｉｕｍｉｎＭｅｄｉｃｉｎｅ．ＷａｓｈｉｎｇｔｏｎＤＣ：ＮａｔｉｏｎａｌＡｃａｄｅｍｙＰｒｅｓｓ，１９９２．３９－４３，５７－６１，６７－７８２刘国正，刘伯里．锝、铼五配位化合物的构型．核化学与放射化学，１９９７，１９（３）：２８－２９３刘国正，刘伯里．锝化学研究Ⅷ．晶体中锝、铼配合物的构型与键长变化规律．核化学与放射化学，１９９５，１７（２）：８０－９０４ＤａｖｉｓｏｎＡ，ＤｅｐａｍｐｈｉｌｉｓＢＶ，ＪｏｎｅｓＡＧ，ｅｔａｌ．ＳｙｎｔｅｓｉｓａｎｄＣｈａｒａｃｔｅｒｉｚａｔｉｏｎｏｆＣｏｍｐｌｅｘｅｓＣｏｎｔａｉｎｉｎｇｔｈｅＢｉｓ（１，２－ｄｉｏｌａｔｏ）ｏｘｏｔｅｃｈｎｅｔｉｕｍ（Ⅴ）Ｃｏｒｅ．ＩｎｏｒｇＣｈｉｍＡｃｔａ，１９８７，１２８：１６１－１６７５ＲｏｃｈｏｎＦＤ，ＭｅｌａｎｓｏｎＲ，ＫｏｎｇＰＣ．ＳｔｒｕｃｔｕｒｅｏｆＢｉｓ（４－ｎｉｔｒｏ－１，２－ｃａｔｅｃｈｏｔａｔｏ）ｏｘｏｔｅｃｈｎｅｔｉｕｍ（Ⅴ）．ＡｃｔａＣｒｙｓｔ，１９９２，Ｃ４８：７８５－７８８６ＡｂｒａｍｓＭＪ，ＬａｒｓｅｎＳＫ，ＺｕｂｉｅｔａＪ．ＩｎｖｅｓｔｉｇａｔｉｏｎｏｆｔｈｅＴｅｃｈｎｅｔｉｕｍ－ｈｙｄｒａｚｉｄｏＣｏｒｅ．ＳｙｎｔｈｅｓｉｓａｎｄＳｔｒｕｃ－ｔｕｒａｌＣｈａｒａｃｔｅｒｉｚａｔｉｏｎｏｆ[（ｎ－Ｃ４Ｈ９）４Ｎ][Ｔｃ２（ＮＮＰｈ２）２（Ｃ６Ｃｌ４Ｏ２）４]·ＣＨ２Ｃｌ２·２ＣＨ３ＯＨ，ａＴｃ（Ⅴ）／Ｔｃ（Ⅵ）ＣａｔｅｃｈｏｌａｔｅＣｏｍｐｌｅｘＷｉｔｈＴｈｅＨｙｄｒａｚｉｄｏＬｌｉｇａｎｄｓＡｄｏｐｔｉｎｇｔｈｅＵｎｕｓｕａｌη１ＢｒｉｄｇｉｎｇＭｏｄｅ．ＩｎｏｒｇＣｈｅｍ，１９９１，３０：２０３１－２０３５７ＢａｌｄａｓＪ，ＣｏｌｍａｎｅｔＳＦ，ＭａｃｋａｙＭＦ．ＰｒｅｐａｒａｔｉｏｎａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｓｏｆ[ＡｓＰｈ４]·[Ｔｃ４Ｎ４Ｏ２（ｏｘ）６]ａｎｄ[ＡｓＰｈ４]２[ＴｃＯ（ｏｘ）（Ｈｏｘ）]·３Ｈ２Ｏ：ＴｅｃｈｎｅｔｉｕｍＣｏｍｐｌｅｘｅｓＣｏｎｔａｉｎｉｎｇＱｕａｄｒｉｄｅｎｔａｔｅｏｒＵｎｉｄｅｎｔａｔｅＯｘａｌａｔｏＬｉｇａｎｄｓ．ＪＣｈｅｍＳｏｃ，ＤａｌｔｏｎＴｒａｎｓ，１９８８，（７）：１７２５８ＳｔｅｉｇｍａｎＪ，ＭｅｉｎｋｅｎＧ，ＲｉｃｋａｒｄｓＰ．ＲｅｄｕｃｔｉｏｎｏｆＰｅｒｔｅｃｈｎｅｔａｔｅ－９９ｂｙＳｔａｎｎｏｕｓＣｈｌｏｒｉｄｅ．Ｉ．ＳｔｏｉｃｈｉｏｍｅｔｒｙｏｆｔｈｅＲｅａｃｔｉｏｎｉｎＨｙｄｒｏｃｈｌｏｒｉｃＡｃｉｄ，ｉｎａＣｉｔｒａｔｅＢｕｆｅｒ，ａｎｄｉｎａＤＴＰＡｂｕｆｅｒ．ＩｎｔＪＡｐｐｌＲａｄｉａｔＩｓｏｔ，１９７５，２６：６０１－６０９９ＨｗａｎｇＬＬＹ，ＲｏｎｃａＮ，ＳｏｌｏｍｏｎＮＡ，ｅｔａｌ．ＣｏｍｐｌｅｘｅｓｏｆＴｅｃｈｎｅｔｉｕｍＷｉｔｈＰｏｌｙｈｙｄｒｉｃＬｉｇａｎｄｓ．ＩｎｔＪＡｐｐｌＲａｄｉａｔＩｓｏｔ，１９８５，３６：４７５－４８０１０ＳｔｅｉｇｍａｎＪ，ＨｗａｎｇＬ，ＳｒｉｖａｓｔａｖａＳ．ＣｏｍｐｌｅｘｅｓｏｆＲｅｄｕｃｔｅｄＴｅｃｈｎｅｔｉｕｍ－９９ＷｉｔｈＰｏｌｙｈｙｄｒｉｃＣｏｍｐｏｕｎｄｓ．ＪＬａｂｅｌｅｄＣｏｍｐｄＲａｄｉｏｐｈａｒｍ，１９７７，１３：１６０１１ＳｔｅｉｇｍａｎＪ，ＭｅｉｎｋｅｎＧ，ＲｉｃｈａｒｄｓＰ．ＴｈｅＲｅｄｕｃｔｉｏｎｏｆＰｅｒｔｅｃｈｎｅｔａｔｅ－９９ｂｙＳｔａｎｎｏｕｓＣｈｌｏｒｉｄｅⅡ．ＴｈｅＳｔｏ－ｉｃｈｉｏｍｅｔｒｙｏｆｔｈｅＲｅａｃｔｉｏｎｉｎＡｑｕｅｏｕｓＳｏｌｕｔｉｏｎｏｆＳｅｖｅｒａｌＰｈｏｓｐｈｏｒｕｓ（Ⅴ）Ｃｏｍｐｏｕｎｄｓ．ＩｎｔＪＡｐｐｌＲａｄｉａｔＩｓｏｔ，１９７８，２９：６５３－６６０１２ＲｕｓｓｅｌＣＤ，ＣａｓｈＡＧ．ＯｘｄａｔｉｏｎＳｔａｔｅｏｆＴｅｃｈｎｅｔｉｕｍｉｎＢｏｎｅＳｃａｎｎｉｎｇＡｇｅｎｔｓａｓＤｅｔｅｒｍｉｎｅｄａｔＣａｒｉｅｒＣｏｎｃｅｎｔｒａｔｉｏｎｂｙＡｍｐｅｒｏｍｅｔｒｉｃＴｉｔｒａｔｉｏｎ．ＩｎｔＪＡｐｐｌＲａｄｉａｔＩｓｏｔ，１９７９，３０：４８５－４８８１３ＤｅｐａｍｐｈｉｌｉｓＢＶ，ＪｏｎｅｓＡＧ，ＤａｖｉｓｏｎＡ．Ｌｉｇａｎｄ－ｅｘｃｈａｎｇｅＲｅａｃｔｉｖｉｔｙＰａｔｅｒｎｓｏｆＯｘｏｔｅｃｈｎｅｔｉｕｍ（Ⅴ）Ｃｏｍ－ｐｌｅｘｅｓ．ＩｎｏｒｇＣｈｅｍ，１９８３，２２：２２９２－２２９７１４ＭｕｅｎｚｅＲ．ＦｏｒｍａｔｉｏｎｏｆＣｉｔｒａｔｅＣｏｍｐｌｅｘｅｓｏｆＴｅｃｈｎｅｔｉｕｍ．ＲａｄｉｏｃｈｅｍＲａｄｉｏａｎａｌＬｅｔ，１９７７，３０：６１－６４１５ＪｕｒｉｓｓｏｎＳ，ＢｅｒｎｉｎｇＤ，ＪａｉＷ，ｅｔａｌ．ＣｏｏｒｄｉｎａｔｉｏｎＣｏｍｐｏｕｎｄｓｉｎＮｕｃｌｅａｒＭｅｄｉｃｉｎｅ．ＣｈｅｍＲｅｖ，１９９３，９３：１１３７－１１５６
计量
- 文章访问数: 213
- HTML全文浏览量: 0
- PDF下载量: 700
下载:
