Ring-Opening Reaction of a Pergermylated Platinacyclopentane Forming 1,4-Bis(arenethiolato)tetragermanes

Abstract

Pergermylated platinacyclopentane, having four dibutylgermylene groups, [Pt(GenBu2GenBu2GenBu2GenBu2)(dmpe)] (1, dmpe = 1,2-bis(dimethylphosphino)ethane), reacted with 2-fold diaryl or dialkyl sulfides to yield 1,4-bis(thiolato)tetragermanes, RS(GenBu2)4SR (R = C6H4tBu-4, C6H4Me-4, C6H5, C6H4Cl-4, C6F5, nBu), in 61–91% yields. Bis(thiolato)platinum complexes [Pt(SR)2(dmpe)] were also obtained as byproduct in 47–98% yields. An equimolar reaction of (SC6F5)2 with 1 resulted in ring-opening to produce the complex with thiolatotetragermyl and thiolato ligands, [Pt(SC6F5){(GenBu2)4SC6F5}(dmpe)]. Further addition of (SC6H4tBu-4)2 formed an unsymmetrical 1,4-bis(thiolato)tetragermane, C6F5S(GenBu2)4SC6H4tBu-4, and a platinum complex, [Pt(SC6F5)(SC6H4tBu-4)(dmpe)], with two different thiolato ligands at the beginning. These two compounds in the mixtures were gradually converted to [Pt(SC6F5)2(dmpe)] and 4-tBuC6H4S(GenBu2)4SC6H4tBu-4, which was caused by exchange of the thiolato groups. The absorption and fluoresc...