Premium
Synthesis, Characterization, and Dynamic Behaviour of Triosmium Clusters Containing the Tridentate Ligand {Ph 2 PCH 2 CH 2 } 2 S (PSP)
Author(s) -
Persson Roger,
Stchedroff Marc J.,
Gobetto Roberto,
Carrano Carl J.,
Richmond Michael G.,
Monari Magda,
Nordlander Ebbe
Publication year - 2013
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201201403
Subject(s) - chemistry , osmium , thioether , ligand (biochemistry) , moiety , stereochemistry , medicinal chemistry , cluster (spacecraft) , isomerization , crystallography , cluster chemistry , nuclear magnetic resonance spectroscopy , molecule , ruthenium , organic chemistry , biochemistry , receptor , computer science , programming language , catalysis
Reaction of [Os 3 (CO) 11 (NCMe)] with bis‐diphenylphosphanylethylene sulfide, {Ph 2 PCH 2 CH 2 } 2 S (PSP), leads to the formation of [Os 3 (CO) 11 (PSP)] and [{Os 3 (CO) 11 } 2 (μ‐PSP)] in good yield. Similarly, treatment of [Os 3 (CO) 10 (NCMe) 2 ] with PSP affords the cluster [Os 3 (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 [Os 3 (CO) 11 (PSP)] with [Os 3 (CO) 10 (NCMe) 2 ] yields the compound 1,2‐[{Os 3 (CO) 11 }(μ 3 ‐PSP){Os 3 (CO) 10 }] in which the thioether moiety and one of the phosphane groups of the PSP ligand are coordinated equatorially to the {Os 3 (CO) 10 } subunit. The cluster 1,2‐[{Os 3 (CO) 11 }(μ 3 ‐PSP){Os 3 (CO) 10 }] is also formed when [Os 3 (CO) 11 (PSP)] is oxidatively decarbonylated by reaction with trimethylamine N ‐oxide. The metastable cluster 1,2‐[{Os 3 (CO) 11 }(μ 3 ‐PSP){Os 3 (CO) 10 }] undergoes slow isomerisation at room temperature to form 1,1‐[{Os 3 (CO) 11 }(μ 3 ‐PSP){Os 3 (CO) 10 }] in which the thioether and phosphane moieties coordinate in a chelating mode to one of the {Os 3 (CO) 10 } subunits with the thioether moiety in an axial position. The dynamic behaviour of these clusters has been investigated by variable‐temperature 13 C{ 1 H} and 13 P{ 1 H} NMR spectroscopy. The solid‐state structures of [{Os 3 (CO) 11 } 2 (μ‐PSP)] and [Os 3 (CO) 10 (μ‐PSP)] are reported.