No abstract

Reactions of (NBu)[TcOCl] or [TcCl(PPh)(CHCN)] with in situ-prepared lithium arylselenolates and -tellurolates give (NBu)[TcO(ArE)] (E = Se, Te; Ar = phenyl) and [Tc(ArE)(PPh)(CHCN)] (E = Se, Te; Ar = phenyl, 2,6-Mephenyl, mesityl) complexes, respectively. The products contain square-pyramidal (Tc compounds) and trigonal bipyramidal (Tc complexes) coordinated technetium atoms. Density functional theory calculations indicate that the Tc-chalcogen bonds in the Tc compounds have a greater bond order than those in the Tc compounds.

Keywords: Tellurium / Ligand design / Palladium / Platinum / Mercury / Solid-state structures N-[3-(Phenyltellanyl)propyl]picolinamide (HL1) or N-[NЈЈ,NЈЈ-methyl(phenyl)aminothiocarbonyl]-NЈ-[3-(phenyltellanyl)propyl]benzamidine (HL2) react with equivalent amounts of PtCl 2 or PdCl 2 with formation of neutral [MCl(L1-κN,NЈ,Te)] or [MCl(L2-κS,N,Te)] chelates. A corresponding reaction of HL2 with HgCl 2 results in the formation of [HgCl 2 (HL2-κS,Te)]. Treatment of [PtCl(L1-N,NЈ,Te)] with elemental iodine results in the exclusive oxidation of the metal [a] Scheme 2. Synthesis of HL1 and HL2.Both products were obtained as viscous oils, which could not be solidified even after several chromatographic purifi-Eur.

Phenyltelluroxane clusters of the composition [{(PhTe) 19 O 24 } 2 I 18 (solv)] (1)a re formed during the hydrolysis of [PhTeI 3 ] 2 or the oxidation of various phenyltellurium(II) compounds with iodine under hydrolytic conditions.T he compounds consist of two half-spheres with a{(PhTe) 19 O 24 } 9+ network, which are connected by 18 iodine atoms.T he spherical clusters can accommodate solvent molecules such as pyridine or methanol in the center of two rings formed by iodine atoms.T he presence of other metal ions during the cluster formation results in as elective replacement of the central {PhTe} 3+ units of eachh alf-sphere as has been demonstrated with the isolation of [{(PhTe) 18 ({Ca-(H 2 O) 2 }O 24 } 2 I 16 ]( 2)a nd [{(PhTe) 18 ({Y(NO 3 )(H 2 O)}O 24 } 2 I 16 ] (3). Acrownether-like coordination by six oxygen atoms of the telluroxane network is found for the {Ca(H 2 O} 2 } 2+ and {Y-(NO 3 )(H 2 O)} 2+ building blocks.M ass spectrometric studies show that considerable amounts of the intact clusters are transferred to the gas phase without dissociation.

Phenyltelluroxane clusters of the composition [{(PhTe) 19 O 24 } 2 I 18 (solv)] (1)a re formed during the hydrolysis of [PhTeI 3 ] 2 or the oxidation of various phenyltellurium(II) compounds with iodine under hydrolytic conditions.T he compounds consist of two half-spheres with a{(PhTe) 19 O 24 } 9+ network, which are connected by 18 iodine atoms.T he spherical clusters can accommodate solvent molecules such as pyridine or methanol in the center of two rings formed by iodine atoms.T he presence of other metal ions during the cluster formation results in as elective replacement of the central {PhTe} 3+ units of eachh alf-sphere as has been demonstrated with the isolation of [{(PhTe) 18 ({Ca-(H 2 O) 2 }O 24 } 2 I 16 ]( 2)a nd [{(PhTe) 18 ({Y(NO 3 )(H 2 O)}O 24 } 2 I 16 ] (3). Acrownether-like coordination by six oxygen atoms of the telluroxane network is found for the {Ca(H 2 O} 2 } 2+ and {Y-(NO 3 )(H 2 O)} 2+ building blocks.M ass spectrometric studies show that considerable amounts of the intact clusters are transferred to the gas phase without dissociation.