Synthesis and reactivity of triosmium nitrite clusters containing some functionalised amine ligands

Reaction of [Os3(μ-H)(CO)10(μ-η2-NO2)] 1 with ammonia and some amines [2-phenylethylamine, octadecylamine, 4-tert-butylcyclohexylamine, piperidine-1-ethanamine (pipea) and 1-ethynylcyclohexylamine (echa)] afforded a pair of isomers a and b with general formula [Os3(μ-H)(CO)9(μ-η2-NO 2)(NH2R)], R = H 2a and 2b, CH2CH2Ph 3a and 3b, (CH2)17CH3 5a and 5b, (C6H10)But-4 6a and 6b, pipea 7a and 7b or echa 10a and 10b. Carbonylation of isomers 3a and 3b afforded [Os3(μ-H)(CO)10(μ-NHCH2CH2Ph)] 4. Thermolysis of 7a and 7b afforded [Os3(μ-H)(CO)10-(μ-pipea - H)] 8 and [Os3(μ-H)(CO)9(μ-η2-pipea - H)] 9. Thermolysis of 10a resulted in hydride migration, from the metal core to the unsaturated carbons in the organic moiety, to give [Os3(CO)9(μ-η2-NO2)(echa + H)] 11. All these clusters were fully characterised by solution spectroscopic methods and the solid state structures of 2a, 4,5a, 7b, 8, 9 and 11 were determined by X-ray crystallography.