15610-19-2Relevant academic research and scientific papers
Synthesis, characterization, and dynamic behaviour of triosmium clusters containing the tridentate ligand {Ph2PCH2CH 2}2S (PSP)
Persson, Roger,Stchedroff, Marc J.,Gobetto, Roberto,Carrano, Carl J.,Richmond, Michael G.,Monari, Magda,Nordlander, Ebbe
, p. 2447 - 2459 (2013)
Reaction of [Os3(CO)11(NCMe)] with bis-diphenylphosphanylethylene sulfide, {Ph2PCH2CH 2}2S (PSP), leads to the formation of [Os 3(CO)11(PSP)] and [{Os3(CO)11} 2(μ-PSP)] in good yield. Similarly, treatment of [Os 3(CO)10(NCMe)2] with PSP affords the cluster [Os3(CO)10(μ-PSP)], in which the two phosphanes of the PSP ligand coordinate to different osmium atoms of the same triosmium unit. Reaction of [Os3(CO)11(PSP)] with [Os3(CO) 10(NCMe)2] yields the compound 1,2-[{Os 3(CO)11}(μ3-PSP){Os3(CO) 10}] in which the thioether moiety and one of the phosphane groups of the PSP ligand are coordinated equatorially to the {Os3(CO) 10} subunit. The cluster 1,2-[{Os3(CO)11} (μ3-PSP){Os3(CO)10}] is also formed when [Os3(CO)11(PSP)] is oxidatively decarbonylated by reaction with trimethylamine N-oxide. The metastable cluster 1,2-[{Os 3(CO)11}(μ3-PSP){Os3(CO) 10}] undergoes slow isomerisation at room temperature to form 1,1-[{Os3(CO)11}(μ3-PSP){Os 3(CO)10}] in which the thioether and phosphane moieties coordinate in a chelating mode to one of the {Os3(CO)10} subunits with the thioether moiety in an axial position. The dynamic behaviour of these clusters has been investigated by variable-temperature 13C{1H} and 13P{1H} NMR spectroscopy. The solid-state structures of [{Os3(CO) 11}2(μ-PSP)] and [Os3(CO) 10(μ-PSP)] are reported. New clusters coordinated by the tridentate ligand {Ph2PCH2CH2}2S have been synthesised and structurally characterised. A new example of a nondestructive rearrangement of a P,S-bridged triosmium cluster that involves a sulfur carbonyl exchange route is reported. Copyright
