The solid-gas reactions of the ''lightly stabilized'' Os-3(CO)(11)L (L = NCCH3 (1), L = C2H4 (2)) clusters with gaseous reactants as CO, NH3, and H-2 have been investigated. At 80 degrees C polycrystalline samples (ca. 50 mg) of 1 and 2 undergo substitution of the axially bound acetonitrile ligand and the equatorially coordinated ethene ligand by the gaseous reactants. 1 and 2 react with (CO)-C-13 to form Os-3(CO)(11)((CO)-C-13) (3a), but no site selectivity is observed for the labeled carbonyl ligand (as shown by C-13 MAS NMR). On reaction with NH3 both 1 and 2 afford OS3(CO)(11)(NH3) (4) with the ammonia ligand coordinated in an axial position. The observed stereochemistry of the reaction products of 1 and 2 with CO and NH3 suggests the presence of an unsaturated intermediate Os-3(CO)(11), which displays an intramolecular axial-equatorial exchange of the vacant coordination site. Reaction with dihydrogen of solid OS3-(CO)(11)(NCCH3) (1) or Os-3(CO)(11)(C2H4) (2) gives H2Os3(CO)(11) as first product, which under the experimental conditions affords Os-3(CO)(12) and H2Os3(CO)(10).

SOLID-GAS REACTIONS OF THE LIGHTLY STABILIZED OS-3(CO)(11)L(L=NCCH3, C2H4) CLUSTERS WITH CO, NH3, AND H-2

AIME, Silvio;DASTRU', Walter;GOBETTO, Roberto;SAPPA, Enrico
1995

Abstract

The solid-gas reactions of the ''lightly stabilized'' Os-3(CO)(11)L (L = NCCH3 (1), L = C2H4 (2)) clusters with gaseous reactants as CO, NH3, and H-2 have been investigated. At 80 degrees C polycrystalline samples (ca. 50 mg) of 1 and 2 undergo substitution of the axially bound acetonitrile ligand and the equatorially coordinated ethene ligand by the gaseous reactants. 1 and 2 react with (CO)-C-13 to form Os-3(CO)(11)((CO)-C-13) (3a), but no site selectivity is observed for the labeled carbonyl ligand (as shown by C-13 MAS NMR). On reaction with NH3 both 1 and 2 afford OS3(CO)(11)(NH3) (4) with the ammonia ligand coordinated in an axial position. The observed stereochemistry of the reaction products of 1 and 2 with CO and NH3 suggests the presence of an unsaturated intermediate Os-3(CO)(11), which displays an intramolecular axial-equatorial exchange of the vacant coordination site. Reaction with dihydrogen of solid OS3-(CO)(11)(NCCH3) (1) or Os-3(CO)(11)(C2H4) (2) gives H2Os3(CO)(11) as first product, which under the experimental conditions affords Os-3(CO)(12) and H2Os3(CO)(10).
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AIME S; DASTRU W; GOBETTO R; KRAUSE J; SAPPA E
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2318/38033
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