Characteristic Reactivties and Functions of Metal Complexes containing Hypodentate Ligands.

亚齿配基是一种配位原子少于最大可能数目的配位原子与金属中心键合的配位。本研究的目的是制备各种新的含此类配体的配合物，并研究它们的反应活性和功能特性。特别是，由于利用非配位的配体部分来控制光物理性质，我们特别关注了发光配合物。用三(2-吡啶甲基)胺(TPA)和N，N，N‘，N’-四(2-吡啶甲基)乙二胺(TPEN)等多吡啶配体得到的结果如下：(1)与这些配体形成的一系列平面铂(II)和钯(II)配合物都具有非配位臂。自由和配位武器的交换顺序为：铂(二)和钯(二)。(Ii)合成了发光的[Re(CO)_3(TPA)]^+，它也有一个不与配位臂交换的非配位臂。(3)与含三齿TPA的Reo-TPA配合物不同，TPA的V^&lt；IV&Gt；O配合物具有完全配位的TPA(四齿酸)，但与Tpen的V^&lt；IV&Gt；O配合物中分离得到了含低齿配体的配合物。以双膦配体Ph_2P(CH_2)_nPPh_2(n=1-5)为配体，合成了一系列含单齿双膦配体的六茂金属发光簇合物。对于六茂金属单元，我们还成功地引入了大配体游离碱的吡啶基卟啉。我们还使用了一种小的多齿配体，2.5-二巯基-1，3，4-噻二唑(McMTH)。所制备的含单齿单金属MT的配合物分别为[Pt(Terpy)(Mcmt)]^+和[Ru(Terpy)(Bpy)(Mcmt)]^+。它们与另一个铂(特比)单元反应，形成同双核和异双核配合物。此外，还得到了各种类型的McMT配体的铜(I)和银(I)络合物。所有这些McMT络合物都具有很强的发光性能。

Hypodentate ligand is defined as a ligand in which fewer than the maximum possible number of donor atoms are bonded to metal centers. The purpose of the study is to prepare various new complexes containing such ligands and to investigate their reactivities and functional characteristics. In particular we have paid special attention to luminecent complexes as the control of photophysical properties by using uncoordinated ligand moieties are promising. The results obtained by using polypyridyl ligands such as tris(2-pyridylmethyl)amine (tpa) and N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine (tpen) are as follows, (i) A series of planar Pt(II) and Pd(II) complexes with these ligands all have uncoordinated arms. The exchange of the free and coordinated arms have been found in the order Pt(II) < Pd(II) and tpa < tpen. (ii) Luminescent [Re(CO)_3(tpa)]^+ has been prepared which also has one uncoordinated arm that does not undergo exchange with the coordinated ones. (iii) V^<IV>O complexes of tpa has fully coordinated tpa (tetradentate), different from ReO-tpa complexes which have tridentate tpa, but with tpen V^<IV>O complex containing hypodentate ligand has been isolated. With the diphosphine ligands Ph_2P(CH_2)_nPPh_2 (n = 1 - 5), a series of luminescent hexarhenium cluster complexes containing monodentate diphosphines have been obtained. For the hexarhenium unit, we have also successfully introduced giant ligands free base pyridylporphyrines. We have also used a small polydentate ligand, 2.5-dimercapto-1,3,4-thiadiazole(McMTH). The complexes prepared include those containing a monodentate McMT are [Pt(terpy) (McMT)]^+ and [Ru(terpy)(bpy)(McMT)]^+. They react with another Pt(terpy)-unit to form homo and hetero dinuclear complexes. Furthermore various type of Cu(I) and Ag(I) complexes of McMT ligands have been obtained. All these McMT complexes are strongly luminescent.