| In recent decades, boron cluster chemistry has expanded rapidly and developed into a far-reaching area that included neutral boranes and their anions, metallaboranes, carboranes and metallacarboranes, main group heteroboranes and their derivatives. These compounds have provided a lot of interesting potential applications, including solvent extraction, catalysts, boron neutron capture therapy (BNCT), nonlinear optics, liquid crystals, ion-selective electrodes and electrolytes for nonaqueous solvents, interphase transfer of cations, storage batteries and host-guest chemistry. At the same time, the Topological Structure Theory and Polyhedral Skeletal Electron-Pair Theory propelled the further development of borane chemistry and expanded the scope of structural chemistry. Due to the development of the borane chemistry and its structural theory, including the practical utility of the carborane derivatives in many science fields, the study interest on the carborane has been greatly enhanced in recent years. To throw further light on the coordination characteristic of the carborane derivatives containing phosphine ligand and explore their properties and their potential application value, our study interests are concentrated on the carboanyldiphosphine derivative-1,2-(PPh2)2-1,2-C2B10H10. Taken into consideration the above mentioned, it is very significant for the study of carboranyldiphosphine derivative, both for the theoretical study and practical application. The five sections of this thesis are listed as follows.1. We have given a general review about the development of boron chemistry and its potential application, and summarized the study situation of carborane derivatives containing phosphine ligand and their metal complexes.2. 1,2-(PPh2)2-1,2-C2B10H10 has been synthesized and its structure was further confirmed by X-ray diffraction. Three copper complexes with the formula [Cu2(μ-Cl)2(1,2-(PPh2)2-1,2-C2 B10H10)2]·2CH2Cl2(1), [Cu2(μ-Br)2(1,2-(PPh2)2-1,2-C2B10H10)2]·2THF(2) and [Cu2(μ-I)2(1,2- (PPh2)2-1,2-C2B10H10)2](3) were obtained by the reactions of 1,2-(PPh2)2-1,2-C2B10H10 with CuX(X = Cl, Br, I) in ethanol under the reflux conditions. All the complexes have been characterized by elemetal analysis, FT-IR, 1H and 13C NMR spectroscopy and X-ray structure determination. Single crystal structure showed all the complexes contained two Cu atoms, and the two same coordination units (Cu(1,2-(PPh2)2-1,2-C2B10H10)) were connected by two Cl atoms which could function as two bridges. The geometry at the Cu atom was a distorted tetrahedron, in which two positions were occupied by two phosphorous atoms of the PPh2 groups connected to the two C atoms of carborane(Cc), and the other two resulted from two X atoms which bridged the other Cu atom at the same time. The catalytic study of the complex 3 demonstrated that this complex could be used as catalyst in the reaction of the amination of iodobenzene with aniline.The reactions of 1,2-(PPh2)2-1,2-C2B10H10 with AgCl, PdCl2,PdCl2 and KI, and NiBr2·6H2O were also studied. Four complexes containing 1,2-(PPh2)2-1,2-C2B10H10 were obtained, which the formula were [Ag2(μ-Cl)2(1,2-(PPh2)2-1,2-C2B10H10)2]·2CH2Cl2(4), [PdCl2(1,2-(PP h2)2-1,2-C2B10H10)](5), [PdI2(1,2-(PPh2)2-1,2-C2B10H10)](6) and [NiBr2(1,2-(PPh2)2-1,2-C2B10 H10)]·CH2Cl2(7), respectively. For these four complexes, the characterizations of elemetal analysis, FT-IR, 1H and 13C NMR spectroscopy and X-ray structure determination were also studied. The structure of complex 4, which also contained di-μ-Cl-bridged structure, is very similar to the complexes 1 to 3. For complexes 5 to 7, 1,2-(PPh2)2-1,2-C2B10H10 was coordinated bidentately to the metal atom through the two P atoms, therefore a five member chelating ring was formed between the ligand and the metal atom. The coordination sphere of the metal atom was a distorted square planar, in which the other two positions came from two Cl or Br atoms.3. The reactions of 1,2-(PPh2)2-1,2-C2B10H10 with [M(PPh3)2Cl2] (M = Ni, Pd, Pt) were studied in ethanol under the reflux conditions. Three complexes containing the nido- [7,8-(PPh2)2-7,8-C2B9H10]- with similar structures were obtained, which the formula were [NiCl(PPh3){7,8-(PPh2)2-7,8-C2B9H10}](8), [PdCl(PPh3){7,8-(PPh2)2-7,8-C2B9H10}]·1.25CH2 Cl2(9) and [PtCl(PPh3){7,8-(PPh2)2-7,8-C2B9H10}]·2.5CH2Cl2(10), respectively. For the first time, the solvothermal method was introduced into the reaction of the carborane, and we also obtained the complex 10 by the reaction of 1,2-(PPh2)2-1,2-C2B10H10 with [Pt(PPh3)2Cl2] in ethanol under the solvothermal condition. All the complexes were characterized by elemetal analysis, FT-IR, 1H and 13C NMR spectroscopy and X-ray analysis. Single crystal analysis showed that 1,2-(PPh2)2-1,2-C2B10H10 was degraded to nido [7,8-(PPh2)2-7,8-C2B9H10]- anion, and this anion substituted one PPh3 and one Cl- from the starting material [M(PPh3)2Cl2] and thus formed the above three complexes. Due to the steric influence of the large PPh3 group, the coordination sphere of the metal atom was a distorted square planar. Additional, the luminescence property of complex 9 was investigated in CH2Cl2 at room temperature.The reactions of 1,2-(PPh2)2-1,2-C2B10H10 with NiCl2·6H2O in ethanol and PdCl2 in acetonitrile were carried out, and two binuclear complexes with the formula [Ni2(μ-Cl)2{7,8-( PPh2)2-7,8-C2B9H10}2](11) and [Pd2(μ-Cl)2{7,8-(PPh2)2-7,8-C2B9H10}2]·0.25CH2Cl2(12) were obtained. The structure of these two complexes was similar to complexes 1 to 4. The difference was that the carborane skeleton was degraded from closo to nido in these two complexes, while in complexes 1 to 4 it maintained its closo skeleton. By treatment PdCl2 and 1,2-(PPh2)2-1,2-C2B10H10 in cyanophenyl other than in acetonitrile, we obtained the complex [Pd{7,8-(PPh2)2-7,8-C2B9H10}2]·4CHCl3(13), whose structure was different from the complex 12 because the two Cl- were all substituted by two nido [7,8-(PPh2)2-7,8-C2B9H10]- anion.The four tetranuclear gold cluster: [Au4{7,8-(PPh2)2-7,8-C2B9H10}2(PPh3)2](14) was obtained by the reaction of 1,2-(PPh2)2-1,2-C2B10H10 with [Au(PPh3)NO3] in THF under the stirring condition. Single crystal structure showed that four gold atoms formed a tetrahedral framework. Among these four gold atoms, two were chelated by two nido carborane diphosphine [7,8-(PPh2)2-7,8-C2B9H10]- anions coming from the degradation of 1,2-(PPh2)2- 1,2-C2B10H10, respectively, while the other two were ligated to two PPh3 groups. The luminescence property of cluster 14 was also investigated in dichloromethane solution at room temperature.4. The reactions of 1,2-(PPh2)2-1,2-C2B10H10 with metal compounds NiCl2·6H2O, CuCl2·2 H2O and ZnCl2 in ethanol with no protection of dry N2 under the stirring conditions were studied. Four complexes with the formula [Ni{7-(OPPh2)-8-(PPh2)-7,8-C2B9H10}{7,8-(PPh2)2- 7,8-C2B9H10}](15), [Ni(THF){7,8-(OPPh2)2-7,8-C2B9H10}2]·THF(16), [Cu{7,8-(OPPh2)2-7,8- C2B9H10}2](17) and [Zn{7,8-(OPPh2)2-7,8-C2B9H10}2](18), respectively, were obtained, in which the 1,2-(PPh2)2-1,2-C2B10H10 was oxidized and degraded. The obtaining of the compounds 1-(OPPh2)-2-(PPh2)-1,2-C2B10H10 and H[7,8-(OPPh2)2-7,8-C2B9H10]·0.25C2H5OH proved that 1,2-(PPh2)2-1,2-C2B10H10 could also be oxidized and degraded by the oxygen in air with no presence of the metal ion. All the four complexes and two free carborane phosphine oxide compounds were characterized by elemetal analysis, FT-IR, 1H and 13C NMR spectroscopy and X-ray structure determination. Single crystal analysis demonstrated that the 1,2-(PPh2)2-1,2-C2B10H10 could be oxidized and degraded with or without the metal ion, and a further conclusion could be drawn from the structures of complexes 15, 16 and two carborane phosphine oxide compounds that the oxidization and degradation process of the 1,2-(PPh2)2-1,2-C2B10H10 could be orderly described as the oxidization of one phosphorus atom, the degradation of the closo carborane skeleton and the oxidization of another phosphorus atom.5. The reactions of 1,2-(PPh2)2-1,2-C2B10H10 with (NH4)2MS4 (M = Mo, W) and M'SCN (M'= Cu, Ag) were studied. Under the protection of dry N2, treatment CuSCN or AgSCN, (NH4)2MoS4 or (NH4)2WS4 and 1,2-(PPh2)2-1,2-C2B10H10 with a molar ratio 2:1:4 in CH2Cl2, four heterobimetallic clusters with trinuclear M'2M core were obtained. The formula of these clusters were as follows: [Cu2MS4(1,2-(PPh2)2-1,2-C2B10H10)2] (M = Mo(19), W(21)), [Ag2M S4(1,2-(PPh2)2-1,2-C2B10H10)2] (M = Mo(24), W(25)). With an aim to know if the product of the reaction could be affected by the temperature, we carried out the reaction of CuSCN, (NH4)2MoS4 and 1,2-(PPh2)2-1,2-C2B10H10 in CH2Cl2 with the ratio 2:1:4 under the reflux condition. The cluster [Cu2MoS4(1,2-(PPh2)2-1,2-C2B10H10)2]·CH2Cl2(20), with same structural type to cluster 19 but with different crystal system and space group, was obtained. All the clusters have been characterized by elemetal analysis, FT-IR, UV/Visible, 1H and 13C NMR spectroscopy and X-ray structure determination. X-ray diffraction showed that the central M atom was directly bonded to two Cu or Ag atoms and three metal atoms (two M'atoms and one M atom) were almost in a linear conformation. 1,2-(PPh2)2-1,2-C2B10H10 was bidentately coordinated to the M'atom through its two phosphorus atoms to fulfill the metal's four coordinates.Treatment 1,2-(PPh2)2-1,2-C2B10H10, CuSCN (AgSCN) and (NH4)2MOS3 (M = Mo, W) under the similar conditions to the preparation of the above clusters, we obtained four heterobimetallic trinuclear clusters: [Cu2MOS3(1,2-(PPh2)2-1,2-C2B10H10)2](M = Mo(22), W(23)) and [Ag2MoOS3(1,2-(PPh2)2-1,2-C2B10H10)2](26), [Ag2WS4(1,2-(PPh2)2-1,2-C2B10H10 )2](27). Due to the O atom of the staring material (NH4)2WOS3 was substituted by one S atom, the formula of cluster 27 was same to cluster 25, but their structures were completely different. For clusters 22, 23 and 27, X-ray diffraction data demonstrated that the central MOS32- or WS42-, as tetradentate ligand, was coordinated to the two Cu(Ag) atoms, and the difference from the above five clusters was the conformation of the cluster core was butterfly-shaped other than a linear one. In addition, the cluster [Ag2WS4(1,2-(PPh2)2-1,2-C2B10H10)2](27) has been found to show luminescence property induced by ligand to ligand charge transfer (LLCT) in CH2Cl2 solution at room temperature.In summary, some characteristics of these type's reactions and coordination rules related to 1,2-(PPh2)2-1,2-C2B10H10 and [7,8-(PPh2)2-7,8-C2B9H10]- have been discovered during the synthesis and structural study of the carboranyldiphosphine metal complexes. The property studies on part of the complexes implied that some complexes might have practical application value in certain fields. |
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