Sulfur Family Of Carborane Ligands Organic Multinuclear Transition Metal Complexes Synthesis And Structural Studies

In this dissertation, a series of heteronuclear organometallic compounds with 1,2-dichalcogenolato-1,2-dicarba-closo-dodecaborane ligands had been synthesized and characterized, and forty-one complexes were determined through X-ray single crystal diffraction analysis. Conclusions were summarized as follows:1,A number of mononuclear 16-electron Cp^tt and Cp* half-sandwich complexes of Rhodium containing a bidentate, chelating 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolato ligand had been synthesized and characterized. X-ray structure revealed that there was a "pseudoaromatic" metalladichalcogenolene five-membered ring. These complexes could serve as promising precursors for the synthesis of mixed-metal clusters, due to both their unsaturation at the metal atom and the bridging or chelating properties of the sulfur or selenium atoms respectively.The half-sandwich rhodium complexes [Cp'Rh{E₂C₂(B₁₀ H₁₀ )}] [Cp' = Cp*,E = S(1a), Se(1b); Cp' = Cp^tt, E = S(2a), Se(2b)] reacted with Fe(CO)₅ and 2 equiv of Me₃NO to afford the binuclear RhFe complexes [Cp'Rh{E₂C₂(B₁₀ H₁₀ )}]-{Fe(CO)₃}[Cp' = Cp*, E = S(3a), Se(3b); Cp' = Cp^tt, E = S(4a), Se(4b)]. The trinuclear RhCo₂ complexes [Cp'Rh{E₂C₂(B₁₀ H₁₀ )}]{Co₂(CO)₅}[Cp' = Cp*, E = S(5a), Se(5b); Cp' = Cp^tt, E = S(6a), Se(6b)] were obtained form the reaction of 1a,b,2a,b with Co₂(CO)₈ and Me₃NO. X-ray structure revealed that there was a closed RhCo₂ triangular core containing of two Rh-Co bonds and one Co-Co bond.2,A series of heterometallic compounds containing Rh-M(Mo,W) bond had been synthesized and characterized by reactions of the half-sandwich rhodium complex [Cp'Rh{E₂C₂(B₁₀ H₁₀ )}] [Cp' = Cp*, E = S(1a), Se(1b); Cp' = Cp^tt, E = S(2a), Se(2b)] with Mo(CO)₃(py)₃/W(CO)₃(py)₃ in the presence of BF₃·Et₂O. X-ray structure revealed that Rh atoms had been reduced from Rh^â…¢to Rh^â…¡by the fragment Mo(CO)₃/W(CO)₃, at the same time the Rh-M (Mo,W) bond existed.3,The half-sandwich rhodium complexes[Cp^ttRh{E₂C₂(B¹⁰ H¹⁰ )}] [E = S(2a), Se(2b)] reacted with Ni(COD)₂ (COD = cyclo-octa-1,5-diene, C₈H₁₂ ) to afford the purple trinuclear compounds {Cp^ttRh[E₂C₂(B₁₀ H₁₀ )]}₂Ni (E = S(17a), Se(17b)). The molecular structures of 17a,17b have been determined by X-ray crystallography.The metallochalcogenolato ligand Cp*Rh(μ-SPh)[E₂C₂(B₁₀ H₁₀ )]ˉ(E = S(18a), Se(18b)) had been synthesized and characterized. The new half-sandwich mixed-metal Rh₂M (M=Ni, Pd) trinuclear complexes bridged by selenoether-selenolatocarborane ligands [Cp*Rh{μ-Se₂C₂(B₁₀ H₁₀ )}]₂M[μ-Se(C₄H₉) ]₂ [M=Ni, Pd] have been prepared by reactions of the [Cp*Rh{μ-Se₂C₂(B₁₀ H₁₀ )}{μ-Se(C₄H₉) }] anion with NiCl₂ or Pd(PhCN)₂Cl₂, respectively. The molecular structures have been determined by X-ray crystallography.4,The half-sandwich rhodium complexes [Cp*Rh{E₂C₂(B₁₀ H₁₀ )}] [E = S(1a), Se(1b)] reacted with [Ru(COD)Cl₂] _x to afford the binuclear Rh/Ru complexes {Cp*Rh(μ-Cl)₂[μ-E₂C₂(B₁₀ H₁₀ )]Ru(COD)} (E = S(23a), Se(23b)). The reaction in the base environment could afford the product [Cp*RhS₂C₂(B₁₀ H₁₀ )][Ru(COD)] with Ru-Rh bond. Several low valence Rhodium compounds as the starting material to get the mixed valence multirhodium compounds. [Cp*RhS₂C₂(B₁₀ H₁₀ )]-[(μ-Cl)Rh(COD)](26) could be synthesized by reaction of the half-sandwich rhodium complex [Cp*Rh{S₂C₂(B₁₀ H₁₀ )}] with the [Rh(COD)Cl]₂．The reaction of 1b with [Rh(CO)₂Cl]₂ gave the zigzag tetranuclear compound {Cp*Rh[Se₂C₂(B₁₀ H₁₀ )]}(μ-CO) [Rh₂Se₂C₂(B₁₀ H₁₀ )](27) , the molecular structures have been determined by X-ray crystallography.5,Four new dichalcogenolate carborane bridged binuclear rhodium(â… ) complexes [Rh₂(COD)₂(μ₂-E₂C₂(B₁₀ H₁₀ ))] [COD = cycloocta-1,5-diene (C₈H₁₂ ), E = S(28a), Se(28b)] and [Rh₂(CO)₄(μ₂-E₂C₂(B₁₀ H₁₀ ))] [E = S(29a), Se(29b)] have been prepared by reactions of the dilithium dichalcogenolate carboranes Li₂E₂C₂B₁₀ H₁₀ (E = S, Se) with [Rh(COD)Cl]₂ or [Rh(CO)₂Cl]₂, respectively. Treatments of complex 28a, 28b with carbon monoxide replacing with the chelating olefin could also afford dimeric complexes 29a, 29b.6,Three half-sandwich binuclear transition metal complexes containing the Cab^C,C chelate ligands (Cab^C,C=C₂B₁₀ H₁₀ ) had been synthesized and characterized. Chloride complex with LiSPh gave [Cp*Rh(μ-SPh)]₂(Cab^C,C). In addition, X-ray structure analyses were performed on complexes where the potential C,C-chelate ligand, a goodσ-donor ligand, was found to coordinate in a bidentate mode as a bridge.