Please use this identifier to cite or link to this item: http://scholarbank.nus.edu.sg/handle/10635/94671
Title: Reactions of [Pt2(μ-S)2(PPh3)4] with Group 6 and 7 metal carbonyls; Crystal structure of the apparently unsaturated heterometallic complex [Pt2Re(μ3-S)2(PPh3) 4(CO)3]+
Authors: Liu, H.
Jiang, C.
Yeo, J.S.L. 
Mok, K.F. 
Liu, L.K.
Hor, T.S.A. 
Yan, Y.K.
Keywords: Heterometallic
Metalloligand
Platinum
Rhenium
Sulfide
Tungsten
Issue Date: 15-Feb-2000
Citation: Liu, H.,Jiang, C.,Yeo, J.S.L.,Mok, K.F.,Liu, L.K.,Hor, T.S.A.,Yan, Y.K. (2000-02-15). Reactions of [Pt2(μ-S)2(PPh3)4] with Group 6 and 7 metal carbonyls; Crystal structure of the apparently unsaturated heterometallic complex [Pt2Re(μ3-S)2(PPh3) 4(CO)3]+. Journal of Organometallic Chemistry 595 (2) : 276-284. ScholarBank@NUS Repository.
Abstract: Reaction of [Pt2(μ-S)2(PPh3)4] (1) with a mixture containing [Re2(CO)10], Me3NO·2H2O and MeOH at room temperature affords an oxidative methoxylation complex, [Pt2Re2(μ-OMe)2(μ3-S) 2(PPh3)4(CO)6] (2), and a Pt-Re heterometallic salt, [Pt2Re(μ3-S)2(PPh3) 4(CO)3]+[Re3(μ 3-OMe)(μ-OMe)3(CO)9]- (3a). The core of the cation of 3a comprises a {Pt2ReS2} trigonal bipyramidal 'cluster' with weak Pt-Re bonding interactions and an apparently unsaturated Re(I) atom. The [BF4]- salt of this cation, 3b, can be prepared by the reaction of 1 with [Re(CO)5(H2O)][BF4], and the Mn analogue, [Pt2Mn(μ3-S)2(PPh3) 4(CO)3][BF4] (4), can be similarly synthesised using [Mn(FBF3)(CO)5]. Addition of 1 to [M(I)2(CO)3(NCMe)2] (M=Mo, W) is accompanied by iodide migration to give the salts [Pt2M(μ3-S)2I(PPh3) 4(CO)4][M(I)3(CO)4] (M=Mo, 5; W, 6a). With [Mo(CO)4(NCMe)2], 1 undergoes reductive carbonylation and desulfurization to give [Pt2(μ-S)(PPh3)3(CO)] (7). The above reactions represent the first examples of 1 as a metalloligand towards carbonyl complexes of the less electron-rich transition metals, and demonstrate that addition reactions of 1 can be complicated by ligand dissociation, ligand migration, or reductive desulphurization. The crystal structures of compounds 3a and 3b were determined. © 2000 Elsevier Science S.A.
Source Title: Journal of Organometallic Chemistry
URI: http://scholarbank.nus.edu.sg/handle/10635/94671
ISSN: 0022328X
Appears in Collections:Staff Publications

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