From a Trinuclear Platinum(III) Phosphido Derivative to a Platinum(II) Cluster: Formation of a P-C Bond
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- 作者：Juan Fornié ; s ; Consuelo Fortuñ ; o ; Susana Ibá ; ñ ; ez ; and Antonio Martí ; n
- 刊名：Inorganic Chemistry
- 出版年：2006
- 出版时间：June 12, 2006
- 年：2006
- 卷：45
- 期：12
- 页码：4850 - 4858
- 全文大小：206K
- 年卷期：v.45,no.12(June 12, 2006)
- ISSN：1520-510X
文摘
Reaction of the trinuclear PtIII-PtIII-PtII [(C6F5)2PtIII(
-PPh2)2PtIII(-PPh2)2Pt(C6F5)2] (2) derivative with NBu4Br orNBu4I results in the formation of the trinuclear PtII complexes [NBu4][(PPh2C6F5)(C6F5)Pt(-PPh2)(-X)Pt(-PPh2)2Pt(C6F5)2] [X = I (3), Br (4)] through an intramolecular PPh2/C6F5 reductive coupling and the formation of thephosphine PPh2C6F5. The trinuclear PtII complex [(PPh2C6F5)(C6F5)Pt(-PPh2)Pt(-PPh2)2Pt(C6F5)2] (5), which displaystwo Pt-Pt bonds, can be obtained either by halide abstraction in 4 or by refluxing of 2 in CH2Cl2. This latterprocess also implies an intramolecular PPh2/C6F5 reductive coupling. Treatment of complex 5 with several ligands(Br-, H-, and CO) results in the incorporation of the ligand to the cluster and elimination of one (X = H-) or both(X = Br-, CO) Pt-Pt bonds, forming the trinuclear complexes [NBu4][(PPh2C6F5)(C6F5)Pt(-PPh2)(-X)Pt(-PPh2)2Pt(C6F5)2] [X = Br (6), H (7)] or [(PPh2C6F5)(C6F5)Pt(-PPh2)2Pt(-PPh2)(CO)Pt(C6F5)2(CO)] (8). The structures ofthe complexes have been established on the basis of 1H, 19F, and 31P NMR data, and the X-ray structures of thecomplexes 2, 3, 5, and 7 have been established. The chemical relationship between the different complexes hasalso been studied.
-PPh2)2PtIII(-PPh2)2Pt(C6F5)2] (2) derivative with NBu4Br orNBu4I results in the formation of the trinuclear PtII complexes [NBu4][(PPh2C6F5)(C6F5)Pt(-PPh2)(-X)Pt(-PPh2)2Pt(C6F5)2] [X = I (3), Br (4)] through an intramolecular PPh2/C6F5 reductive coupling and the formation of thephosphine PPh2C6F5. The trinuclear PtII complex [(PPh2C6F5)(C6F5)Pt(-PPh2)Pt(-PPh2)2Pt(C6F5)2] (5), which displaystwo Pt-Pt bonds, can be obtained either by halide abstraction in 4 or by refluxing of 2 in CH2Cl2. This latterprocess also implies an intramolecular PPh2/C6F5 reductive coupling. Treatment of complex 5 with several ligands(Br-, H-, and CO) results in the incorporation of the ligand to the cluster and elimination of one (X = H-) or both(X = Br-, CO) Pt-Pt bonds, forming the trinuclear complexes [NBu4][(PPh2C6F5)(C6F5)Pt(-PPh2)(-X)Pt(-PPh2)2Pt(C6F5)2] [X = Br (6), H (7)] or [(PPh2C6F5)(C6F5)Pt(-PPh2)2Pt(-PPh2)(CO)Pt(C6F5)2(CO)] (8). The structures ofthe complexes have been established on the basis of 1H, 19F, and 31P NMR data, and the X-ray structures of thecomplexes 2, 3, 5, and 7 have been established. The chemical relationship between the different complexes hasalso been studied.