Please use this identifier to cite or link to this item: https://doi.org/10.1021/om049407t
Title: [(L n)Ru{η 3-(tpdt)}] complexes as dithiolate donors to group 10 metal centers: Synthetic, single-crystal X-ray diffraction and electrochemical studies {L n = η 6-C 6Me 6 (HMB) and η 5-C 5Me 5 (Cp*); tpdt = S(CH 2CH 2S) 2}
Authors: Shin, R.Y.C.
Tan, G.K.
Koh, L.L.
Goh, L.Y. 
Webster, R.D.
Issue Date: 20-Dec-2004
Source: Shin, R.Y.C., Tan, G.K., Koh, L.L., Goh, L.Y., Webster, R.D. (2004-12-20). [(L n)Ru{η 3-(tpdt)}] complexes as dithiolate donors to group 10 metal centers: Synthetic, single-crystal X-ray diffraction and electrochemical studies {L n = η 6-C 6Me 6 (HMB) and η 5-C 5Me 5 (Cp*); tpdt = S(CH 2CH 2S) 2}. Organometallics 23 (26) : 6108-6115. ScholarBank@NUS Repository. https://doi.org/10.1021/om049407t
Abstract: Trinuclear mixed metal cationic complexes of Ru-Pd, [{(L n)Ru(μ-η 2:η 3-tpdt)} 2Pd] 2+ (4A, L n = HMB; 8, L n = Cp*), and of Ru-Pt, [{(L n)Ru(μ-η 2: η 3-tpdt)} 2Pd] 2+ (5B, L n = HMB; 9, L n = Cp*), containing bare bridging M(II) (M = Pd, Pt) centers, are formed from the reaction of [(HMB) Ru II(η 3-tpdt)] (1) and [Cp*Ru III(η 3-tpdt)] (2) (tpdt ≡ S(CH 2CH 2S) 2) with Pd(MeCN) 2Cl 2 (or PdCl 2) and PtCl 2, respectively. With Pt(PPh 3) 2Cl 2, both 1 and 2 displace the chloro ligands, thus forming dinuclear complexes [{(HMB)Ru(μ-η 2: η 3-tpdt)}{Pt(PPh 3) 2}] 2+ (6) and [{(Cp*)Ru(μ-η 2:η 3-tpdt)}{Pt(PPh 3) 2] 2+ (10), in which Pt is coordinated to two thiolate atoms and two PPh 3 ligands in a four-coordinate planar geometrical environment. X-ray diffraction analyses show that the arene complexes 4A and 5B also possess four-coordinate planar geometry at the central metal atom. In the Cp* complexes, the central MS 4 moiety is tetrahedral for M = Pd, but planar for M = Pt, both metal centers being metal-metal bonded to the peripheral Ru atoms, presumably as dictated by the demands of the 18e rule. Electrochemical studies show that complexes 8 and 9 and the Ni analogues of 4A and 8, viz., 3 and 7, respectively, can be reduced in two one-electron steps and oxidized by one electron. The one-electron reduced and oxidized species are paramagnetic, and EPR spectra were obtained of the species in frozen solutions. The electrochemical data indicate that the Pd- and Pt-containing compounds show intermediate electron delocalization between the two Ru atoms, indicative of a class II system, while the Ni-containing analogues show extensive electron delocalization between the Ru atoms, indicative of a class III system.
Source Title: Organometallics
URI: http://scholarbank.nus.edu.sg/handle/10635/92880
ISSN: 02767333
DOI: 10.1021/om049407t
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