| Since 1912, borane chemistry has made a further progress 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 nuclear medicine, pharmacology, radioactive waste treatment, polymer science, 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 utilities of the carborane derivatives in many science fields, the study interests on the carborane have been greatly enhanced in recent years. To throw further light on the coordination characteristic of the carborane derivatives containing phosphine ligands and explore their properties and their potential applications value, our study interests are concentrated on the carboanyldiphosphine derivatives-1,2-(PR2)2-1,2-C2B10H10(R = Ph, iPr, Cy). Taken into consideration the above mentioned, it is very significant for the study of carboranyldiphosphine derivative, both for the theoretical studies and practical applications.The four sections of this thesis are listed as follows.1. The development of boron chemistry and its potential applications and the study situation of carborane derivatives containing phosphine ligand and their metal complexes are reviewed.2. The reactions of 1,2-(PPh2)2-1,2-C2B10H10 with HgCl2 were studied in ethanol or dichloromethane under the reflux conditions. Three complexes [Hg{7,8-(PPh2)2-7,8-C2B9 H10}2]·CH2Cl2(1), [HgCl2{1,2-(PPh2)2-1,2-C2B10H10}]2·3HgCl2·2CH2Cl2(2) and [HgCl2{1,2 -(PPh2)2-1,2-C2B10H10}]2·3HgCl2·CH2Cl2·2H2O(3) were obtained. All the complexes were characterized by elemetal analysis, FT-IR, 1H and 13C NMR spectroscopy and X-ray analysis. Single crystal analysis showed that the Hg atom in complex 1 was coordinated to P atoms of two nido [7,8-(PPh2)2-7,8-C2B9H10]- anion, forming the distorted tetrahedron. Complexes 2 and 3 all form a 1D chain coordination polymer via bridged Cl-Hg bonds, which is the first supramolecular complex formed by Cl-Hg bonds. The geometry of all the mercury atoms involved can be classed in two types, the four-coordinate mercury and the six-coordinate mercury, formed tetrahedron and octahedron, respectively.The complex [HgCl(PPh3){7,8-(PPh2)2-7,8-C2B9H10}](4) was obtained from the reaction of 1,2-(PPh2)2-1,2-C2B10H10 with [Hg(PPh3)2Cl2] in ethanol under the reflux conditions. The complex was 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-C2B10 H10 is degraded to nido [7,8-(PPh2)2-7,8-C2B9H10]- anion. The Hg atom was coordinated to the two P atoms of [7,8-(PPh2)2-7,8-C2B9H10]-, one Cl atom and one P of the PPh3 group completed the tetrahedron of Hg. The 1D chain is formed through C-H…Cl hydrogen bonds, then the adjacent 1D chains are linked into 3D network via the C-H…H-B dihydrogen bonds.The reaction of 1,2-(PPh2)2-1,2-C2B10H10 with Zn(OAc)2 in ethanol under the solvothermal condition was also studied, and complex [Zn{7,8-(OPPh2)2-7,8-C2B9H10}2]·2 CH3CH2OH(5) was obtained, which has been characterized by elemetal analysis, FT-IR, 1H and 13C NMR spectroscopy and X-ray analysis. Single crystal analysis showed that the 1,2-(PPh2)2-1,2-C2B10H10 was oxidized and degraded, the Zn atom was coordinated with four O atoms forming a distorted tetrahedron.3. Three copper complexes [Cu2(μ-Cl)2(1,2-(PiPr2)2-1,2-C2B10H10)2](6), [Cu2(μ-Br)2(1,2- (PiPr2)2-1,2-C2B10H10)2](7) and [Cu2(μ-I)2(1,2-(PiPr2)2-1,2-C2B10H10)2](8) were obtained by the reactions of 1,2-(PiPr2)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, 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-(PiPr2)2-1,2-C2B10 H10)) were connected by two Cl atoms which could function as two bridges. The geometry of the Cu atom was a distorted tetrahedron, in which two positions were occupied by two phosphorous atoms of the PiPr2 groups connected to the two C atoms of carborane(Cc). Two halogen atoms bridge the metal centers forming a dimer structure [Cu2(μ-X)2(1,2-(P iPr2)2-1,2-C2B10H10)2], which are linked into 2D supramolecular networks through novel C-H…H-B dihydrogen bonding interactions. The C-H group of isopropyl acting as the hydrogen donor has not been reported in the previous papers.The reactions of 1,2-(PiPr2)2-1,2-C2B10H10 with AgCl, NiCl2, NiBr2·6H2O and HgCl2 were also studied. Four complexes containing 1,2-(PiPr2)2-1,2-C2B10H10 were obtained, the formula were [Ag2(μ-Cl)2(1,2-(PiPr2)2-1,2-C2B10H10)2](9), [NiCl2(1,2-(PiPr2)2-1,2-C2B10 H10)]·2CH2Cl2(10), [NiBr2(1,2-(PiPr2)2-1,2-C2B10H10)](11) and [HgCl2(1,2-(PiPr2)2-1,2-C2 B10H10)](12), 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 9, which also contained di-μ-Cl-bridged structure, was very similar to the complexes 6 to 8. For complexes 10-12, 1,2-(PiPr2)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 of complexes 10, 11 was a distorted square planar, in which the other two positions came from two Cl or Br atoms. While for complex 12, the metal atom was in a distorted tetrahedron coordinated geometry.The reactions of 1,2-(PiPr2)2-1,2-C2B10H10 with (NH4)2MoS4 and MSCN (M = Cu, Ag) were studied and two heterobimetallic clusters with trinuclear M2Mo core [Cu2MoS4(1,2- (PiPr2)2-1,2-C2B10H10)2](13) and [Ag2MoS4(1,2-(PiPr2)2-1,2-C2B10H10)2]·1.5CH2Cl2(14) were obtained. These two 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 Mo atom was directly bonded to two Cu or Ag atoms. 1,2-(PiPr2)2-1,2-C2B10H10 was bidentately coordinated to the M atom through its two phosphorus atoms to fulfill the metal's four coordinates. The reaction of 1,2-(PiPr2)2-1,2-C2B10H10 and Zn(OAc)2 in ethanol with no protection of dry N2 under the stirring conditions was studied. The complex with the formula [Zn{7,8-(OPiPr2)2-7,8-C2B9H10}2](15) was obtained, in which the 1,2-(PiPr2)2-1,2-C2B10H10 was oxidized and degraded. The complex was characterized by elemetal analysis, FT-IR spectroscopy 1H and 13C NMR spectroscopy and X-ray structure determination. Single crystal analysis demonstrated that the 1,2-(PiPr2)2-1,2-C2B10H10 could be oxidized and degraded with the metal ion, Zn atom was coordinated to four O atoms, forming a distorted tetrahedron.4. 1,2-(PCy2)2-1,2-C2B10H12 has been synthesized and its structure was confirmed by X-ray diffraction. The reaction of 1,2-(PCy2)2-1,2-C2B10H10 with CuX(X = Cl, Br, SCN) in ethanol with the protection of dry N2 under the reflux conditions were studied, which gave us three complexes: [Cu2(μ-Cl)2(1,2-(PCy2)2-1,2-C2B10H10)2](16), Cu2(μ-Br)2(1,2-(PCy2)2- 1,2-C2B10H10)2](17), [Cu2(μ-SCN)2(1,2-(PCy2)2-1,2-C2B10H10)2]·3CH3CH2OH(18). While complex [Cu2(μ-SCN)2(1,2-(PCy2)2-1,2-C2B10H10)2](19) was obtained from the reaction of 1,2-(PCy2)2-1,2-C2B10H10 and CuSCN in dichloromethane. All the complexes have been characterized by elemetal analysis, FT-IR spectroscopy and X-ray structure determination. Single crystal structure showed that these four complexes contained two Cu cores, the two same units (Cu(1,2-(PCy)2-1,2-C2B10H10)) were bridged by two X or SCN. The Cu atom was in a distorted tetrahedron geometry, and two points were X or SCN, the other two were the P atoms from the 1,2-(PCy2)2-1,2-C2B10H12. The structures of 18 and 19 were isomeric compounds.The reaction of 1,2-(PCy2)2-1,2-C2B10H10 and AgCl, NiBr2 in dichloromethane with the protection of dry N2 under the reflux conditions were studied, and two complexes [Ag2(μ-Cl)2(1,2-(PCy2)2-1,2-C2B10H10)2](20) and [NiBr2(1,2-(PCy2)2-1,2-C2B10H10)2](21) were obtained. These two complexes have been characterized by elemetal analysis, FT-IR, 1H and 13C NMR spectroscopy and X-ray structure determination. Single crystal structure showed that complexes 20 and 21 held the same structure with 16 and 11, respectively. The coordination sphere of Ag atom was a distorted tetrahedron in complex 20, which of the Ni atom was a distorted square planar in complex 21. Some characteristics of these type's reactions and coordination rules related to 1,2-(PR)2-1,2-C2B10H10(R = Ph, iPr, Cy) and [7,8-(PPh2)2-7,8-C2B9H10]- have been discovered during the synthesis and structural study of the carboranyldiphosphine metal complexes, we also found the influence of the steric effect and the solvent.
|
PDF Full Text Request