Reaction of [Os3(CO)11(NCMe)] with bis-diphenylphosphanylethylene sulfide, {Ph2PCH2CH2}2S (PSP), leads to the formation of [Os3(CO)11(PSP)] and [{Os3(CO)11}2(-PSP)] in good yield. Similarly, treatment of [Os3(CO)10(NCMe)2] with PSP affords the cluster [Os3(CO)10(-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-[{Os3(CO)11}(3-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}(3-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-[{Os3(CO)11}(3-PSP){Os3(CO)10}] undergoes slow isomerisation at room temperature to form 1,1-[{Os3(CO)11}(3-PSP){Os3(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(-PSP)] and [Os3(CO)10(-PSP)] are reported.
Synthesis, Characterization, and Dynamic Behaviour of Triosmium Clusters Containing the Tridentate Ligand {Ph2PCH2CH2}2S (PSP) / Roger Persson;Marc J. Stchedroff;Roberto Gobetto;Carl J. Carrano;Michael G. Richmond;Magda Monari;Ebbe Nordlander. - In: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. - ISSN 1434-1948. - STAMPA. - 2013:(2013), pp. 2447-2459. [10.1002/ejic.201201403]
Synthesis, Characterization, and Dynamic Behaviour of Triosmium Clusters Containing the Tridentate Ligand {Ph2PCH2CH2}2S (PSP)
MONARI, MAGDA;
2013
Abstract
Reaction of [Os3(CO)11(NCMe)] with bis-diphenylphosphanylethylene sulfide, {Ph2PCH2CH2}2S (PSP), leads to the formation of [Os3(CO)11(PSP)] and [{Os3(CO)11}2(-PSP)] in good yield. Similarly, treatment of [Os3(CO)10(NCMe)2] with PSP affords the cluster [Os3(CO)10(-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-[{Os3(CO)11}(3-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}(3-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-[{Os3(CO)11}(3-PSP){Os3(CO)10}] undergoes slow isomerisation at room temperature to form 1,1-[{Os3(CO)11}(3-PSP){Os3(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(-PSP)] and [Os3(CO)10(-PSP)] are reported.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.