Based On The Reaction Of The Organometallic Cobalt, Rhodium, Iridium, The Assembly Of The Sixteen E-carborane Compounds And Metal Bonding

The chemistry of carborane was one of the most active research fields in modern chemistry. Functionalized carborane and its complexes are useful model complexes which are widely used in the organometallic catalytic reactions and boron neutron capture therapy (BNCT) of cancer treatment. In addition, they exhibit inimitable applications in molecular recognition, nonlinear optical properties and LCD materials due to their special physical and chemical nature. For this reason, to design and synthesize new types of carborane complexes, which are the core problem of carborane chemistry research, has been receiving intensive attention by scientists. This thesis is focused on the following four aspects based on the 16-electron carborane complexes Cp^*M[E₂C₂(B₁₀H₁₀)] (M = Co, Rh, Ir; E = S, Se).(1) The study of the reactions between 16-electron half-sandwich complex Cp^*Co[S₂C₂(B₁₀H₁₀)] and polydentate ligands. According to previous study, 16 electron pseudo-aromatic complexes with 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolato ligands exhibit electron deficiency at central metal atoms. They can react with rich-electron donor ligands to form 18-electron structures. In this paper, two types of bidentate ligands (pyrazine , 4,4'-bipyridine , trans-1,2-bis(4-pyridyl)-ethylene (bpe) and 2,5-bis(4-pyridyl)-1,3,5-oxadiazole) (bpo)) and two types of tridentate ligands (2,4,6-tri(4-pyridyl)-1,3,5-triazine (tpt) and 2,4,6-tri[(4-pyridyl)-sulfanylmethyl]-1,3,5-triazine (tpst)) were chosen to react with Cp^*Co[S₂C₂(B₁₀H₁₀)]. The results show that the complexes 4a, 5a, 6a from reactions of pyrazine, 4,4'-bipyridine, bpe and Cp^*Co[S₂C₂(B₁₀H₁₀)] have similar transform structure. However, complex 7a derived from bpo adopts cis arrangemet. Similarly, complex 8a and 9a which have different types of ligands also show different structures.(2) The study of the reactions between 16-electron half-sandwich complexs Cp^*M[E₂C₂(B₁₀H₁₀)] (M = Co, Rh, Ir; E = S, Se) and low valent transition metal complex [Ru(COD)Cl₂]_x under base conditions. When Cp^*Ir[S₂C₂(B₁₀H₁₀)] and [Ru(COD)Cl₂]_x were stirred with excessive NaHCO₃ at 35-40℃, the carborane cage opened complexes 10a and 11a were isolated as major products, and trinuclear complex 12a and methoxy groups disubstituted complex 13a at the B(3)/B(6) sites of the carborane ligand were isolated as minor products. However, if this reaction was carried out at low temperature, methoxy groups monosubstituted and disubstituted complexes 14a and 13a were isolated as major products, and only a little of carborane cage opened complexes were obtained. The corresponding 16-electron rhodium and cobalt complexes react with [Ru(COD)Cl₂]_x also led to the formation of carborane cage opened complexes, but no trinuclear and substituted complexes have been isolated.(3) The study of the reactions of Cp^*Co[E₂C₂(B₁₀H₁₀)] (E = S, Se) and low valent transition metal complex [Rh(COD)(OMe)]₂ or [Rh(COD)(OEt)]₂. To react Cp^*Co[S₂C₂(B₁₀H₁₀)] with equal [Rh(COD)(OMe)]₂ or [Rh(COD)(OEt)]₂ in the toluene/methanol (1:1), two major products {Cp^*Co[S₂C₂(B₉H₁₀)]}[(COD)Rh] (23a) and [(COD)Rh]₂[S₂C₂(B₁₀H₁₀)] (24a) were isolated; the corresponding selenium complexes {Cp^*Co[Se₂C₂(B₁₀H₁₀)]}[(COD)Rh] (23b) and [(COD)Rh]₂[Se₂C₂(B₁₀H₁₀)] (24b) were obtained under the same conditions. Complex 23a was a hetero-binuclear Co-Rh complex with carborane cage opened, however, the carborane cage was intact in complex 23b.(4) The syntheses and characterization of Co-W clusters with 1,2-dichalcogenolato-o-carborane ligands. The 16-electron complexes Cp^*Co[S₂C₂-(B₁₀H₁₀)] (1a) and CpCo[S₂C₂(B₁₀H₁₀)] (1c) react with W(CO)₃(Py)₃ in the presence of more than three equivalents of BF₃·OEt₂ in diethyl ether to give mixed-metal complexes {Cp^*Co[S₂C₂(B₁₀H₁₀)]}W(CO)₂[S₂C₂(B₁₀H₁₀)] (25a) and {CpCo[S₂C₂-(B₁₀H₁₀)]}W(CO)₂[S₂C₂(B₁₀H₁₀)](25c).