Please use this identifier to cite or link to this item:
Title: Different bonding modes of the C-7 ring on iridium clusters. Synthesis, electrochemistry, and solid state structure of [Ir-6(CO)(13)(mu(3)-eta(2):eta(2):eta(2)-C7H8)], [Ir-6(CO)(12)(mu(3)-eta(2):eta(3):eta(2)-C7H7)](-), and [Ir-6(CO)(12)(mu(3)-eta(2):eta(2):eta(2)-C7H8)](2-)
Authors: Della Pergola, R.
Bianchi, A.
Fabrizi De Biani, Fabrizia 
Garlaschelli, L.
Manassero, M.
Sansoni, M.
Strumolo, D.
Zanello, Piero
Issue Date: 2002
Project: None 
The cluster [Ir6(CO)13(C7H8)] (1) was synthesized from [Ir6(CO)16] and excess cycloheptatriene in refluxing toluene. In the solid state, the six iridium atoms define an octahedral metal cage, and one face is capped by the μ3-η2:η2:η2-C7H8 ligand, which is a six-electrondonor, through the three CC double bonds. Reaction of 1 with Na2CO3 in THF yields [Ir6(CO)12(C7H7)]- (2). In this octahedral anion, the cycloheptatrienyl ring is almost planar and is coordinated to a triangular face in the μ3-η2:η3:η2-fashion. Reaction of 1 or 2 with NaOH in THF yields [Ir6(CO)12(C7H8)]2- (3), in which a μ3-η2:η2:η2-C7H8 is also present. The 1H NMR spectra of 1 and 3 show five signals, which were assigned to the nonequivalent hydrogen atoms by bidimensional experiments. The spectrum of 2 shows a singlet, even at low temperature, in agreement with a highly fluxional ligand. The interconversions of 1 to the anions 2 and 3, respectively, have been followed by electrochemical investigations. The neutral [Ir6(CO)13(C7H8)] proves to undergo a two-electron reduction, which, being accompanied by decarbonylation, affords the dianion [Ir6(CO)12(C7H8)]2-. In turn, the latter undergoes a two-electron oxidation, which followed by deprotonation affords the monoanion [Ir6(CO)12(C7H7)]-.
ISSN: 0276-7333
DOI: 10.1021/om0204437
Appears in Collections:Publications

Show full item record

Page view(s)

Last Week
Last month
checked on May 5, 2021

Google ScholarTM



Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.