Dicarboxylato ligands in OSMIUM CARBONYL (cas 15696-40-9) sawhorse clusters: Chelating vs. bridging

Add time:09/03/2019    Source:sciencedirect.com

Seven new complexes comprising of diosmium(I) tetracarbonyl sawhorse units bound to dicarboxylate anions (DCAs) have been synthesized using microwave heating. Succinic, adipic, pimelic, suberic, tetradecanedioic, and terephthalic acids react with Os3(CO)12 at temperatures ranging from 180 to 205 °C for 12–20 min to produce the osmium sawhorse complexes, which are subsequently reacted with phosphine ligands to replace the labile axial CO ligands. X-ray crystallographic analysis was used to determine the molecular structures of these complexes. Two complexes, those with suberato and tetradecanedioato ligands, are dinuclear species containing Os2 sawhorse molecules with chelating DCAs that form intramolecular loops. The succinato, adipato and pimelato complexes are tetranuclear species consisting of two Os2 sawhorse moieties linked together by two bridging DCAs. Thus the straight-chain hydrocarbon backbone of the DCAs must contain at least six carbon atoms in order for these ligands to prefer to chelate a single Os2 unit instead of forming bridges between multiple Os2 units. The terephthalato complex is a triangular hexanuclear species consisting of a trimer of dimers with three bridging dicarboxylato anions.

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