{"title":"第一排过渡金属化合物中的立体效应和五配位。具有线性四胺配体的化合物","authors":"J. G. Gibson, E. Mckenzie","doi":"10.1039/J19710001029","DOIUrl":null,"url":null,"abstract":"Compounds of MnII, CoII, NiII, CuII and ZnII of the type M(chelate)X2[where chelate =NN′-di-(3-aminopropyl)piperazine; X = one of a variety of anions] are reported. Square-pyramidal five-co-ordinate cations in the compounds [M(chelate)X]X and [M(chelate)X]Y are characterised for the following: where M = CoII, X = Br and I; where M = NiII, X = Cl, Br and possibly NCS; and where M = CuII, X = Cl, Br, I, NCS, and Y = ClO4, PF6. In addition, a five-co-ordinate species Cu(chelate)Cl2 in which the ligand is only terdentate with a free NH2, also is characterised. Four co-ordinate planar [MN4]2+ species also are characterised for NiII, CuII and perhaps CoII. No significant structural data is available for the MnII, FeII, or ZnII species. The structural assignments for the solid compounds rely on X-ray data (powder-pattern correlations with a known three-dimensional structure), i.r. and electronic spectra, and magnetic measurements. Structural studies of solutions in non-aqueous solvents also are reported. These rely on electronic spectra. Specific ion-pairing limits the use of conductivity data. The origin of the five-co-ordinate structures in these compounds is discussed in terms of the peculiar steric effects of the ligand, which is the precursor of a class of homologous ligands, each of which is expected to give five-co-ordinate compounds of these metals.","PeriodicalId":17321,"journal":{"name":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","volume":null,"pages":null},"PeriodicalIF":0.0000,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"10","resultStr":"{\"title\":\"Steric effects and five-co-ordination in first-row transition-metal compounds. Compounds with a linear tetra-amine ligand\",\"authors\":\"J. G. Gibson, E. Mckenzie\",\"doi\":\"10.1039/J19710001029\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Compounds of MnII, CoII, NiII, CuII and ZnII of the type M(chelate)X2[where chelate =NN′-di-(3-aminopropyl)piperazine; X = one of a variety of anions] are reported. Square-pyramidal five-co-ordinate cations in the compounds [M(chelate)X]X and [M(chelate)X]Y are characterised for the following: where M = CoII, X = Br and I; where M = NiII, X = Cl, Br and possibly NCS; and where M = CuII, X = Cl, Br, I, NCS, and Y = ClO4, PF6. In addition, a five-co-ordinate species Cu(chelate)Cl2 in which the ligand is only terdentate with a free NH2, also is characterised. Four co-ordinate planar [MN4]2+ species also are characterised for NiII, CuII and perhaps CoII. No significant structural data is available for the MnII, FeII, or ZnII species. The structural assignments for the solid compounds rely on X-ray data (powder-pattern correlations with a known three-dimensional structure), i.r. and electronic spectra, and magnetic measurements. Structural studies of solutions in non-aqueous solvents also are reported. These rely on electronic spectra. Specific ion-pairing limits the use of conductivity data. The origin of the five-co-ordinate structures in these compounds is discussed in terms of the peculiar steric effects of the ligand, which is the precursor of a class of homologous ligands, each of which is expected to give five-co-ordinate compounds of these metals.\",\"PeriodicalId\":17321,\"journal\":{\"name\":\"Journal of The Chemical Society A: Inorganic, Physical, Theoretical\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":0.0000,\"publicationDate\":\"1971-01-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"10\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of The Chemical Society A: Inorganic, Physical, Theoretical\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.1039/J19710001029\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1039/J19710001029","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 10
摘要
M(螯合物)X2型MnII、CoII、NiII、CuII和ZnII化合物[其中螯合物=NN′-二-(3-氨基丙基)哌嗪;X =多种阴离子中的一种]。化合物[M(螯合物)X]X和[M(螯合物)X]Y中的方-锥体五坐标阳离子的特征如下:其中M = CoII, X = Br和I;其中M = NiII, X = Cl, Br和可能的NCS;其中M = CuII, X = Cl, Br, I, NCS, Y = ClO4, PF6。此外,还有一种五配位的Cu(螯合)Cl2,其配体仅与游离NH2三齿合。四个坐标平面[MN4]2+物种也具有NiII, CuII和CoII的特征。没有关于MnII、FeII和ZnII种的重要结构数据。固体化合物的结构分配依赖于x射线数据(粉末模式与已知三维结构的相关性)、红外光谱和电子光谱以及磁测量。非水溶剂中溶液的结构研究也有报道。这些依赖于电子光谱。特定离子配对限制了电导率数据的使用。根据配体的特殊空间效应讨论了这些化合物中五配位结构的起源,配体是一类同源配体的前体,每一类同源配体都有望得到这些金属的五配位化合物。
Steric effects and five-co-ordination in first-row transition-metal compounds. Compounds with a linear tetra-amine ligand
Compounds of MnII, CoII, NiII, CuII and ZnII of the type M(chelate)X2[where chelate =NN′-di-(3-aminopropyl)piperazine; X = one of a variety of anions] are reported. Square-pyramidal five-co-ordinate cations in the compounds [M(chelate)X]X and [M(chelate)X]Y are characterised for the following: where M = CoII, X = Br and I; where M = NiII, X = Cl, Br and possibly NCS; and where M = CuII, X = Cl, Br, I, NCS, and Y = ClO4, PF6. In addition, a five-co-ordinate species Cu(chelate)Cl2 in which the ligand is only terdentate with a free NH2, also is characterised. Four co-ordinate planar [MN4]2+ species also are characterised for NiII, CuII and perhaps CoII. No significant structural data is available for the MnII, FeII, or ZnII species. The structural assignments for the solid compounds rely on X-ray data (powder-pattern correlations with a known three-dimensional structure), i.r. and electronic spectra, and magnetic measurements. Structural studies of solutions in non-aqueous solvents also are reported. These rely on electronic spectra. Specific ion-pairing limits the use of conductivity data. The origin of the five-co-ordinate structures in these compounds is discussed in terms of the peculiar steric effects of the ligand, which is the precursor of a class of homologous ligands, each of which is expected to give five-co-ordinate compounds of these metals.