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• W2094633027 abstract "The trinuclear cluster H2Os3(CO)10 reacts with phosphino- and arsino-substituted sulphur diimides tBu2E′NSNEtBu2 (E, E′=P, As) to give the addition products H2Os3(CO)10(tBu2E′NSNE′Bu2) (1–3) containing an intact NSN system. In these clusters one of the hydrides is terminal, the other one occupies a bridging position on the metal framework. The X-ray crystal structure analysis of the mixed derivative H2Os3(CO)10(tBu2PNSNAs′Bu2) (2) reveals the cis,trans-configurated sulphur diimide ligand to be coordinated equatorially through the phosphorus atom. The variable-temperature 13C and 1H NMR spectra exhibit a dynamic phenomenon in solution which is interpreted by a cyclic ligand-site exchange involving the two hydrides as well as one axial and one equatorial carbonyl at the hydrogen-bearing osmium atom. The bis(di-t-butylphosphino) derivative 1 is stable only at low temperatures; above 0°C the compound undergoes fragmentation of the NSN system leading to the cluster HOs3(CO)9[PtBu2N(H)S]. Der dreikernige Cluster H2Os3(CO)10 reagiert mit phosphino- und arsinosubstituierten Schwefeldiimiden tBu2E′NSNEtBu2 (E, E′=P, As) zu den Additionsprodukten H2Os3(CO)10(tBu2E′NSNEtBu2) (1–3), die ein intaktes NSN-System enthalten. In diesen Clustern ist einer der Hydridliganden terminal, während der andere eine Br:uckenposition am Metallgerüst einnimmt. Nach der Röntgenstrukturanalysedes gemischten Derivates H2Os3(CO)10(tBu2PNSNAstBu2) (2) ist der cis,trans-konfigurierte Schwefeldiimidligand equatorial über das Phosphoratom gebunden. Die temperaturabhängigen 13C- und 1H-NMR-Spektren zeigen in Lösung ein dynamisches Phänomen, das sich mit einem cyclischen Stellungswechsel der beiden Wasserstoffe und einem axialen sowie einem equatorialen Carbonyl am wasserstofftragenden Osmiumatom interpretieren lässt. Das Bis(di-t-butylphosphino)-Derivat 1 ist nur bei tiefen Temperaturen beständig; oberhalb 0°C erleidet das NSN-System eine Fragmentierung, die zum Cluster HOs3(CO)9-PtBu2N(H)S] führt." @default.
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• W2094633027 date "1985-10-01" @default.
• W2094633027 modified "2023-09-26" @default.
• W2094633027 title "Addition von phosphino- und arsino-substituierten schwefeldiimiden an H2Os3(CO)10: Kristallstruktur und dynamische struktureffekte von H2Os3(CO)10(tBu2PNSNAstBu2). Fragmentierung des NSN-gerüstes in H2Os3(CO)10(tBu2PNSNPtBu2)" @default.
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• W2094633027 doi "https://doi.org/10.1016/0022-328x(85)87468-4" @default.
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