Synthesis and structural characterization of the [[Rh(5)(CO)(14)]-(H(2)N(CH(2))(4)NH(2))-[Rh(5)(CO)(14)])](2-) and [Rh(5)(CO)(13)(H(2)N(CH(2))(2)NH(2))](-) anions (as [PPh(4)](+) salts): an unprecedented example of carbonyl substitution by alkylamines in a homoleptic metal carbonyl cluster anion.
The substitution of one or two carbonyls by many different primary and secondary alkylamines and -diamines has been established for the first time in a homoleptic carbonyl cluster anion, the trigonal bipyramidal [Rh(5)(CO)(15)](-). Two derivatives, the bis-monosubstituted [[Rh(5)(CO)(14)]-(H(2)N(CH(2))(4)NH(2))-[Rh(5)(CO)(14)]](2-) dianion (1) and the disubstituted chelated [Rh(5)(CO)(13)(H(2)N(CH(2))(2)NH(2))](-) monoanion (2), have been structurally characterized, both in the solid state (as [PPh(4)](+) salts) and in solution, revealing that the sites of the substitution are the cluster apexes. (13)C NMR spectra of 2 revealed localized fluxionality of the CO ligands over the temperature range 298-183 K.
Fumagalli
Alessandro
A
Dipartimento di Biologia Strutturale e Funzionale dell'Università dell'Insubria, Via J. H. Dunant 3, 21100 Varese, Italy. alessandro.fumagalli@uninsubria.it
Malatesta
Maria Carlotta
MC
Tentori
Anna
A
Monti
Diego
D
Macchi
Piero
P
Sironi
Angelo
A