Metal complexes as ligands—IV [1,2,3]: Bi- and Tri- nuclear complexes derived from metal complexes of tetradentate salicylaldimines
Metal complexes as ligands—IV [1,2,3]: Bi- and Tri- nuclear complexes derived from metal complexes of tetradentate salicylaldimines
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作为配体的金属配合物 — IV [1,2,3]：衍生自四齿水杨醛亚胺金属配合物的双核和三核配合物
DOI：
10.1016/0022-1902(68)80357-4
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发表时间：
1968
期刊：
影响因子：
--
通讯作者：
E. Sinn
中科院分区：
文献类型：
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作者：
S. Gruber;C. Harris;E. Sinn
利用水杨醛或邻羟基苯乙酮四齿席夫碱(TSB)金属(M)络合物中两个顺式氧原子的给体性质，合成了一系列双核和三核配合物。金属卤化物M‘X_2[M’铜(II)或锌(II)]或金属高氯酸盐M‘(ClO_4)_n[M’Cu(II)，Ni(II)，Fe(II)，Al(III)，Mg(II)，Ca(II)，Sr(II)，Ba(II)，Na(I)，或Ag(I)形成一般类型的[MTSb)M‘X2]和M’(MTSb)2(ClO4)n的配合物，其中许多是水合的。许多化合物的低磁矩是由于金属之间的反铁磁相互作用造成的。虽然许多[(MTSB)M‘Xn]类型的络合物是非离子的，但M’(MTSB)2(ClO4)n在硝基苯溶液中具有预期的电导率。络合物CuTSb的磁矩和光谱吸收的系统性趋势是由于铜原子的平面向准四面体环境的空间扭曲增加，因为连接TSb(-O)中相邻氮原子的碳链的长度(R)增加了。NRN……O-)增加。光谱表明，[(CuTSb)(CuCl2)]中的氯键铜原子随着CuTSb中的铜原子以相同的方式发生扭曲而逐渐从平面构型向四面体构型转变，直至两个伪四面体铜原子的距离太近。正如预期的那样，当溴原子取代此类化合物中的氯原子时，这种扭曲似乎略大一些。在给定的[CuTSB]CuCl2或M‘(CuTSb)2(ClO4)n·xH2 O络合物中，CuTSB内部的铜原子似乎比自由CuTSb更接近平面立体化学.结果表明，单核、双核和三核配合物中金属的立体化学是由配体和金属的空间需求引起的，并且在很大程度上是可以预测的。报道了MTSb及其双核和三核衍生物的一些红外光谱，并重新指定了MTSb的早期吸收光谱。
The detailed synthesis is reported for a series of bi-and tri-nuclear complexes formed by using the donor properties of the two cis-oxygen atoms in metal (M) complexes of tetradentate Shiff bases (TSB) derived from salicylaldehyde or o-hydroxyacetophenone. The “complex ligands”[MTSB, M Cu (II), NiU (II) or Zn (II)] readily react with metal halides M′ X 2 [M′ Cu (II) or Zn (II)] or metal perchlorates M′(ClO 4) n [M′ Cu (II), Ni (II), Fe (II), Al (III), Mg (II), Ca (II), Sr (II), Ba (II), Na (I), or Ag (I) to form the complexes of the general types [MTSB) M′ X 2] and M′(MTSB) 2 (ClO 4) n, many of which are hydrated. The low magnetic moments of a number of the compounds are due to an antiferromaagnetic interactions between the metals. While a number of complexes of type [(MTSB) M′ X n] have previously been reported to be non-ionic, the complexes M′(MTSB) 2 (ClO 4) n are found to have the expected electrical conductivities in nitrobenzene solution. A systematic trend in the magnetic moments and spectral absorptions of the complexes CuTSB is due to an increased steric distortion from a planar towards a pseudo-tetrahedral environment about the copper atom as the length of the carbon chain (R) joining the adjacent nitgrogen atoms in TSB (-O... NRN.... O-) increases. The spectra indicate that the chlorine bonded copper atom in [(CuTSB)(CuCl 2 complexes becomes increasingly distorted from a planar towards a tetrahedral configuration as the copper inside the CuTSB distorts the same way, up to a point where the approach of the two pseudo-tetrahedral copper atoms would be too close. As expected, this distortion appears to be slightly greater when bromine atoms are substituted for chlorine atoms in such compounds. In a given [CuTSB) CuCl 2 or M′(CuTSB) 2 (ClO 4) n· xH 2O complex, the copper atom inside the CuTSB appears to be considerably closer to planar stereochemistry than it is the free CuTSB. It is concluded that the stereochemistries of the metals in the mono-, bi-, and tri-nuclear complexes are due to, and to a large extent predictable from, the steric requirements of the ligands and metals. Some ir spectra of MTSB and the bi-and tri-nuclear derivatives are reported, and earlier assignments of absorptions in the complexes MTSB are re-examined.© 1968.