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|Title:||Electronic communications mediated by metal clusters||Authors:||Yip, J.H.K.
|Issue Date:||2004||Citation:||Yip, J.H.K.,Wu, J.,Wong, K.-Y.,Ho, K.P.,Pun, C.S.-N.,Vittal, J.J. (2004). Electronic communications mediated by metal clusters. Journal of the Chinese Chemical Society 51 (5 B) : 1245-1252. ScholarBank@NUS Repository.||Abstract:||Two model systems [CuI 3(dppm) 3(μ3-η1-C≡CFc)2] ·PF6 (1·PF6) and [PtI 2(dppm)2(C≡CFc)2] (2) were devised to probe the ability of metal clusters in mediating electronic communications. The complexes were characterized by using single-crystal X-ray diffraction, UV-vis spectroscopy, and voltammetry (dppm = bis(diphenylphosphino)methane; Fc = ferrocenyl). The complex is composed a of trimetallic CuI 3 core bridged by three dppm and capped with one and two ferrocenylacetylides, respectively. Cyclic and differential pulse voltammograms of 1·PF 6 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 12+ arises mainly from the reduction of electrostatic repulsion and statistical distribution. On the other hand, the Pt-Pt σ-bond enhances electronic interactions between the terminal Fc-groups in compound 2. The CV of the complex shows two reversible Fc-centered oxidations which are separated by 267 ± 14 mV and the K c is 3.3 × 104 ± 1.5 × 104. Addition of a d10 AuCl/Br fragment to the Pt-Pt bond gives rise to complexes [Pt2(μ-AuX)(dppm)2(C≡CFc)2] [X = Cl (3) and Br (4)]. The two Fc-oxidations are not resolved in the CV of the complexes, indicating that the electronic communication is shut down.||Source Title:||Journal of the Chinese Chemical Society||URI:||http://scholarbank.nus.edu.sg/handle/10635/93716||ISSN:||00094536|
|Appears in Collections:||Staff Publications|
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