Thallium complexes with bridging units

The only new report of a group 7 complex with thallium is the reaction of [Re7C(CO)2i]3 ion with T1PF6 (Equation (92)).94 The thallium adds in a triply bridging fashion opposite to the capping Re(CO)3 unit 99.94 The complex is stable in dichloromethane but dissociates in coordinating solvents. In acetone, infrared data indicated that the complex would be 99% dissociated at concentrations of the cluster of about 10-4M. Addition of halide ions to dichloromethane solutions causes a precipitation of the thallium(i) halide. 

C6C15) with dimethylsulfoxide (DMSO), which leads to the synthesis of [Tl2 Au(C6F5)2 2 p-DMSO 3] or [Tl2 Au(C6Cl5)2 2 h-DMSO 2]ra, respectively.62 The crystal structure of the complex with fluorine shows a monodimensional polymer formed by repetition of [Au--Tl(p-0 = SMe2)3Tl] units, with gold-thallium interactions of 3.2225(6)-3.5182(8), while the pentachlorophenyl derivative contains two bridging DMSO molecules and an additional [Au(C6Cl5)2] anion. In addition, a thallium-thallium interaction of 3.7562(6) A appears in the latter (Fig. 21). 

An unprecedented cyclic structure was found in a rare example of an organo-actinide complex associated via 7r-interactions. The reaction of ThBr4(thf)4 in THF with one equivalent of cyclopentadienyl thallium followed by treatment with three equivalents of KOPr led to the formation of the highly unusual hexanuclear complex [(C5H5)Th2(OPr )v]3, 106 [102]. In the cyclic molecule three dinuclear Th2(OPr )v units are connected by bridging cyclopentadienyl ligands. The... 

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