Halide Addition/Abstraction in Phosphido Derivatives: Isolation of the Thallium and Silver Intermediates
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- 作者：Juan Fornié ; s ; Consuelo Fortuñ ; o ; Susana Ibá ; ñ ; ez ; Antonio Martí ; n
- 刊名：Inorganic Chemistry
- 出版年：2008
- 出版时间：July 7, 2008
- 年：2008
- 卷：47
- 期：13
- 页码：5978 - 5987
- 全文大小：644K
- 年卷期：v.47,no.13(July 7, 2008)
- ISSN：1520-510X
文摘
Reaction of unsaturated (44e− skeleton) [PdPt2(μ-PPh2)2(μ-P2Ph4)(RF)4] 4 with Br− produces the saturated (48e− skeleton) complex [NBu4][(RF)2Pt(μ-PPh2)(μ-Br)Pd(μ-PPh2)(μ-P2Ph4)Pt(RF)2] 5 without any M−M′ bond. Attempts to eliminate Br− of 5 with Ag+ in CH2Cl2 as a solvent gives a mixture of [(RF)2PtIII(μ-PPh2)2PtIII(RF)2] and some other unidentified products as a consequence of oxidation and partial fragmentation. However, when the reaction of 5 with Ag+ is carried out in CH3CN, no oxidation is observed but the elimination of Br− and the formation of [(RF)2(CH3CN)Pt(μ-PPh2)Pd(μ-PPh2)(μ-P2Ph4)Pt(RF)2] 6 (46e− skeleton), a complex with a Pt−Pd bond, takes place. It is noteworthy that the reaction of 5 with TlPF6 in CH2Cl2 does not precipitate TlBr but forms the adduct [(RF)2PtTl(μ-PPh2)(μ-Br)Pd(μ-PPh2)(μ-P2Ph4)Pt(RF)2] 7 with a Pt−Tl bond. Likewise, 5 reacts with [AgOClO3(PPh3)] in CH2Cl2 forming the adduct [AgPdPt2(μ-Br)(μ-PPh2)2(μ-Ph2P-PPh2)(RF)4(PPh3)] 8, which contains a Pt−Ag bond. Both adducts are unstable in a CH3CN solution, precipitating TlBr or AgBr and yielding the unsaturated 6. The treatment of [NBu4]2[(RF)2Pt(μ-PPh2)2Pd(μ-PPh2)2Pt(RF)2] in CH3CN with I2 (1:1 molar ratio) at 233 K yields a mixture of 4 and 6, which after recrystallization from CH2Cl2 is totally converted in 4. If the reaction with I2 is carried out at room temperature, a mixture of the isomers [NBu4][(RF)2Pt(μ-PPh2)(μ-I)Pd(μ-PPh2)(μ-P2Ph4)Pt(RF)2] 9 and [NBu4][(RF)(PPh2RF)Pt(μ-PPh2)(μ-I)Pd(μ-PPh2)2Pt(RF)2] 10 are obtained. The structures of the complexes have been established on the bases of NMR data, and the X-ray structures of 5-8 have been studied. The relationship between the different complexes has been studied.