Formation, Characterization, and Bonding of - and -[PtCl{Te(CH)}], -[PtCl{Te(CH)}], and --[PtCl{Te(CH)}]: Experimental and DFT Study.

[PtCl{Te(CH)}] () was synthesized from the cyclic telluroether Te(CH) and -[PtCl(NCPh)] in dichloromethane at room temperature under the exclusion of light. The crystal structure determination showed that in the solid state, crystallizes as yellow plate-like crystals of the -isomer and the orange-red interwoven needles of . The crystals could be separated under the microscope. NMR experiments showed that upon dissolution of the crystals of in CDCl, it isomerizes and forms a dynamic equilibrium with the -isomer that becomes the predominant species. Small amounts of -[PtCl{Te(CH)}] () and --[PtCl{Te(CH)}] () were also formed and structurally characterized. Both compounds show rare bridging telluroether ligands and two different platinum coordination environments, one exhibiting a -Cl/-Te(CH) arrangement and the other a -Cl/-Te(CH) arrangement. Complex has an open structure with two terminal and two bridging telluroether ligands, whereas complex has a cyclic structure with four Te(CH) bridging ligands. The bonding and formation of the complexes have been discussed through the use of DFT calculations combined with QTAIM analysis. The recrystallization of the mixture of the 1:1 reaction from -DMSO afforded [PtCl{S(O)(CD)}{Te(CH)}] () that could also be characterized both structurally and spectroscopically.