The protonation of [Re7H(C)(CO)21]2- with CF3SO3H in dichloromethane solution produces [Re7H2C(CO)21]- which behaves as a strong acid, being completely dissociated in basic solvents. In acetonitrile the compound loses the capping Re(CO)3 unit, giving the octahedral dianion [Re6H2C(CO)18]2-. The [NEt4]+ salt crystallizes in the monoclinic system, space group P21/c (no. 14), with a = 9.394(3), b = 15.669(3), c = 27.983(6) Å, β = 90.87(3)°, and Z = 4. The structure of the anion is closely related to that of the parent compounds [Re7H(C)(CO)21]2- and [Re7C(CO)21]3-, where a carbon-centred monocapped octahedron of rhenium atoms is surrounded by 21 terminal carbonyl ligands, three for each metal. The two hydride ligands have been indirectly located on the basis of potential-energy computations as double bridging, one on an edge of the basal triangle and the other one on an inter-layer edge. The 1H n.m.r. spectra at low temperature show the presence in solution of three isomers (ratio ca. 1:1.5:10) rapidly exchanging at room temperature. The possible locations of the hydrides in these species are also discussed in the light of the variable-temperature 13C n.m.r. spectra.

Synthesis, solid-state (X-ray) and solution (nuclear magnetic resonance) studies of the hydridocarbido carbonyl cluster anion [re7H2C(CO)21] / T. Beringhelli, G. D'Alfonso, G. Ciani, A. Sironi, H. Molinari. - In: JOURNAL OF THE CHEMICAL SOCIETY DALTON TRANSACTIONS. - ISSN 0300-9246. - :6(1990), pp. 1901-1906.

Synthesis, solid-state (X-ray) and solution (nuclear magnetic resonance) studies of the hydridocarbido carbonyl cluster anion [re7H2C(CO)21]

T. Beringhelli
Primo
;
G. D'Alfonso
Secondo
;
G. Ciani;A. Sironi
Penultimo
;
1990

Abstract

The protonation of [Re7H(C)(CO)21]2- with CF3SO3H in dichloromethane solution produces [Re7H2C(CO)21]- which behaves as a strong acid, being completely dissociated in basic solvents. In acetonitrile the compound loses the capping Re(CO)3 unit, giving the octahedral dianion [Re6H2C(CO)18]2-. The [NEt4]+ salt crystallizes in the monoclinic system, space group P21/c (no. 14), with a = 9.394(3), b = 15.669(3), c = 27.983(6) Å, β = 90.87(3)°, and Z = 4. The structure of the anion is closely related to that of the parent compounds [Re7H(C)(CO)21]2- and [Re7C(CO)21]3-, where a carbon-centred monocapped octahedron of rhenium atoms is surrounded by 21 terminal carbonyl ligands, three for each metal. The two hydride ligands have been indirectly located on the basis of potential-energy computations as double bridging, one on an edge of the basal triangle and the other one on an inter-layer edge. The 1H n.m.r. spectra at low temperature show the presence in solution of three isomers (ratio ca. 1:1.5:10) rapidly exchanging at room temperature. The possible locations of the hydrides in these species are also discussed in the light of the variable-temperature 13C n.m.r. spectra.
Settore CHIM/03 - Chimica Generale e Inorganica
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/185402
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