Thermal C-P and C-H cleavage in co-ordinated phosphines leading to dinuclear platinum complexes and contrasting reactions with M(PPh3)+ (M = Cu, Ag or An) and HgCl2

被引:40
作者
Bender, R
Bouaoud, SE
Braunstein, P
Dusausoy, Y
Merabet, N
Raya, J
Rouag, D
机构
[1] Univ Strasbourg 1, Chim Coordinat Lab, CNRS, UMR 7513, F-67070 Strasbourg, France
[2] Univ Constantine, Inst Chim, Constantine, Algeria
[3] Univ Nancy 1, Fac Sci, Lab Cristallog & Modelisat Mat Mineraux & Biol, UPRESA 7036, F-54506 Vandoeuvre Nancy, France
[4] Univ Strasbourg 1, ULP Bruker, CNRS, UMR 50, F-67070 Strasbourg, France
来源
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1999年 / 05期
关键词
D O I
10.1039/a809448i
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The dinuclear complex [Pt-2(mu-PPh2){mu-(o-C6H4PPh2)}(PPh3)(2)] was prepared by controlled thermolysis of [Pt(C2H4)(PPh3)(2)] and it contains both a diphenylphosphido and an ortho-metallated triphenylphosphine ligand that bridge the Pt-I-Pt-I bond [2.657(1) Angstrom in 3 and 2.677(5) Angstrom in the CH2Cl2 adduct]. Addition of the electrophilic metal reagents [M(PPh3)](+) (M = Cu, Ag or Au) occurs at the Pt-Pt bond, affording [Pt-2{mu-M(PPh3)} (mu-PPh2){mu-(o-C6H4PPh2)}(PPh3)(2)](+) (M = Cu, Ag or Au) whereas selective oxidation by HgCl2 gives the dinuclear platinum(II) complex [Pt2Cl2(mu-PPh2){mu-(o-C6H4PPh2)}(PPh3)(2)] which is shown to have a "mixed-geometry" structure at the metal centres (square planar and flattened tetrahedral). The new complexes have been analysed by P-31-{H-1} and Pt-195 NMR spectroscopy and the structures of three complexes have been determined by X-ray diffraction.
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页码:735 / 741
页数:7
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