REACTIVITY PATTERNS OF THE UNSATURATED TETRAHEDRAL CLUSTER {[RE-4(MU(3)-H)(4)(CO)(12)] - EASY ADDITION OF 4 MECN MOLECULES AND IONIC OR NEUTRAL FRAGMENTATION PATHWAYS OF THE SPIKED-TRIANGLE INTERMEDIATE [RE-4(MU-H)(4)(CO)(12)(NCME)(4)]}
Articolo
Data di Pubblicazione:
1995
Citazione:
REACTIVITY PATTERNS OF THE UNSATURATED TETRAHEDRAL CLUSTER
{[RE-4(MU(3)-H)(4)(CO)(12)] - EASY ADDITION OF 4 MECN MOLECULES AND
IONIC OR NEUTRAL FRAGMENTATION PATHWAYS OF THE SPIKED-TRIANGLE
INTERMEDIATE [RE-4(MU-H)(4)(CO)(12)(NCME)(4)]} / T. BERINGHELLI, G. D'ALFONSO, M. ZARINI. - In: JOURNAL OF THE CHEMICAL SOCIETY DALTON TRANSACTIONS. - ISSN 0300-9246. - :14(1995), pp. 2407-2415.
Abstract:
The unsaturated (56 valence electrons, v.e.s) tetrahedral cluster
{[Re-4(mu(3)-H)(4)(CO)(12)] 1 readily added four acetonitrile
molecules, affording two isomers 2a and 2b of the 64 v.e.s
[Re-4(mu-H)(4)(CO)12- (NCMe)(4)] derivative, containing a
spiked-triangle metallic skeleton. These isomers at room temperature
rapidly underwent an ionic fragmentation to the known unsaturated
triangular cluster anion [Re-3(mu-H)(4)(CO)(9)(NCMe)](-) and to the
cation [Re(CO)(3)(NCMe)(3)](+). The rate of decomposition
significantly increased at low [MeCN] concentration. Treatment of
compounds 2a and 2b with the pi-acidic ligand CO, in the absence of free
acetonitrile, gave only neutral products. Monitoring by NMR spectroscopy
has revealed the rapid stepwise substitution of the nitrile ligands,
accompanied by fragmentation to the known saturated triangular clusters
[Re-3(mu-H)(3)(CO)(12-n)(NCMe)(n)] (n = 1-3) and to the mononuclear
complexes [ReH(CO)(5-n)(NCMe)(n)] (n = 0 or 1). The novel, unstable.
mononuclear hydride [ReH(CO)(4)(NCMe)] has been obtained by treatment
of [ReH(CO)(5)] with Me(3)NO in acetonitrile and by reaction of
[ReH2(CO)(4)](-) with CF3SO3H. in acetonitrile. In the presence of
free acetonitrile, compounds 2a and 2b reacted with CO more slowly and
gave both anionic and neutral triangular clusters.}
Tipologia IRIS:
01 - Articolo su periodico
Elenco autori:
T. BERINGHELLI, G. D'ALFONSO, M. ZARINI
Link alla scheda completa: