Oxidation chemistry of metal-bonded C-4 chains: A combined chemical, spectroelectrochemical, and computational study

Citation
Mi. Bruce et al., Oxidation chemistry of metal-bonded C-4 chains: A combined chemical, spectroelectrochemical, and computational study, J AM CHEM S, 122(9), 2000, pp. 1949-1962
Citations number
75
Categorie Soggetti
Chemistry & Analysis",Chemistry
Journal title
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
ISSN journal
00027863 → ACNP
Volume
122
Issue
9
Year of publication
2000
Pages
1949 - 1962
Database
ISI
SICI code
0002-7863(20000308)122:9<1949:OCOMCC>2.0.ZU;2-Y
Abstract
The known complex {Cp(PPh3)(2)Ru}(2)(mu-C=CC=C) (3-Ph) and its PMe3-substit ution product {Cp(PPh3)(PMe3)Ru}(2)(mu-C=CC=C) (3-Me) have been shown by cy clic voltammetry to undergo a series of four stepwise one-electron oxidatio n processes. Successive oxidation potentials (V) for the first three revers ible processes of 3-Ph (3-Me) are -0.23 (-0.26), +0.41 (+0.33), and +1.03 ( +0.97); the fourth, irreversible oxidation at +1.68 (+1.46) V is accompani ed by chemical transformation followed by further oxidation. Chemical oxida tion of 3-Ph with 1 or 2.5 equiv of AgPF6 in CH2Cl2/1,2-dimethoxyethane gav e the one-and two-electron oxidized species [3-Ph][PF6] and [3-Ph][PF6](2), respectively. The chemical and electrochemical studies have been complemen ted by a series of detailed spectroelectrochemical experiments to obtain sp ectral data associated with the 3(n+) (n = 0-4) species from 1500 To 40 000 cm(-1), without necessitating the isolation of each individual species. Th eoretical techniques have been employed in order to probe the structure of the conjugated all-carbon ligand at each stage of oxidation. Both the metal centers and the carbon atoms of the C-4 bridge are affected, with removal of electrons housed in MOs delocalized over all atoms of the Ru-C-4-Ru chai n. Comparison of models with different ligand surroundings suggests that mo lecules containing strong electron-donating ligands should be more easily o xidized.