Please use this identifier to cite or link to this item: http://hdl.handle.net/10397/19319
Title: Syntheses, structures, and electrochemistry of polynuclear CuI, AgI, and PtII complexes bearing ferrocenyl group
Authors: Yip, JHK
Wu, J
Wong, KY 
Yeung, KW
Vittal, JJ
Issue Date: 2002
Publisher: American Chemical Society
Source: Organometallics, 2002, v. 21, no. 8, p. 1612-1621 How to cite?
Journal: Organometallics 
Abstract: Three polynuclear complexes, [Pt2II(dppm)2(μ-η1:η1-HC=CFc)Cl2] (1), [AgI3(dppm)3(μ3-η1 C≡CFc)]·2CF3SO3 (2·2CF3SO3), and [Cu3I(dppm)3(μ3-η1 -C≡CFc)2]·PF6 (3·PF6), were synthesized and characterized using single-crystal X-ray diffraction, UV-vis spectroscopy, and voltammetry (dppm = bis(diphenylphosphino)methane; Fc = ferrocenyl). Compound 1 is an A-frame complex in which two PtII ions are bridged by two dppm and one ethynylferrocene. Both 2·2CF3SO3 and 3·PF6 are composed of trimetallic Ag3I and Cu3I cores bridged by three dppm and capped with one and two ferrocenylacetylides, respectively. All complexes exhibit reversible Fc oxidation in their cyclic voltammograms (CV), ranging from -48 ± 10 to 235 ± 10 mV vs Ag/AgNO3 (0.1 M). The reduction potential difference between silver and copper complexes is mostly due to intramoleuclar. electrostatic interactions. A weak intervalence charge-transfer transition at 1250 nm arising from the mixed-valence 32+ is observed in the solution near-infrared absorption spectrum of a mixture of 3·PF6 and ferrocenium hexafluo-rophosphate (Cp2FePF6). Cyclic and differential pulse volatmmograms of 3·PF6 show two reversible Fc oxidations separated by 110 ± 14 mV, giving a comproportionation constant Kc of 77 ± 30. The stability of the mixed-valence complex 32+ arises mainly from the reduction of electrostatic repulsion and statistical distribution.
URI: http://hdl.handle.net/10397/19319
ISSN: 0276-7333
EISSN: 1520-6041
DOI: 10.1021/om010998m
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