锝、铼五配位化合物的构型

CONFIGURATION OF FIVE COORDINATED RHENIUM AND TECHNETIUM COMPOUNDS

总结了锝、铼五配位化合物构型的变化规律，并用空腔模型对这些规律进行了解释。铼的五配位化合物皆为高价配合物（氧化态大于四价），在５个配位原子中，当含有１个或５个近距结合原子（带２个或２个以上负电荷的配位原子）时，配合物具有四方锥构型；含有３个近距结合原子时，配合物具有三角双锥构型；含有２个近距结合原子时，配合物具有变形三角双锥构型；含有４个近距结合原子或没有近距结合原子时，五配位结构不稳定。由于锝、铼化学性质相似，这些构型变化规律实际上也是五配位锝化合物的构型变化规律。已测五配位锝化合物的构型种类较少，但都不违反这一构型变化规律。

The configuration selection rules of five coordinated rhenium and technetium compounds have been summarized and further rationalized by cavity model.These five coordinated compounds are all of high oxidation state(>+4).If the coordinating atoms are divided into two groups,close combining atoms with two negative charges or more and normal combining atoms with one or zero negative charge,the configuration selection rules can be expressed as :(1) systems with five or one close combining atoms take a square pyramidal configuration;(2) systems with three close combining atoms take a trigonal bipyramidal configuration;(3) systems with two close combining atoms take a distorted trigonal bipyramidal configuration;(4) systems with four or none close combining atoms are unstable and have not been found yet.