Formation of platinum–carbon σ-bonded complexes from co-ordinated and unco-ordinated olefins and acetylenes

The tetradendate phosphane tris(5H‐dibenzo[a,d]cyclohepten‐5‐yl)phosphane (trop3P, 1) was synthesized from tris(trimethylsilyl)phosphane and 5‐chloro‐5H‐dibenzo[a,d]cycloheptene. Sulfurization of 1 with elemental sulfur led to trop3P=S. Complexes of 1 with AgI, AuI, RhI, IrI, and PdII were prepared. The structures of trop3P (1), trop3P=S (2), [AgCl(trop3P)] (3), [Au(trop3P)(MeCN)]PF6 (5), [RhCl(trop3P)] (6) and [Pd(trop3P)(H2O)](OTf)2 (9) were determined by X‐ray diffraction studies. In the coinage metal complexes, 1 serves as monodentate extremely bulky κ1‐phosphane ligand (cone angle ca. 250°). In the RhI, IrI, and PdII complexes, 1 acts as tetradendate ligand. CP MAS NMR spectroscopy shows that the span of the chemical shift tensor increases in 7, 6, and 9 in this order (Ω = 310 ppm, 410 ppm, 465 ppm) and contains two strongly deshielded components, which are responsible for the unusual high frequency isotropic shift of the 31P resonances. This property correlates inversely with the metal to olefin backbonding (M→C=Ctrop) and δ(31P) decreases with increasing M→C=Ctrop in the order 9 (δ = 260 ppm) > 7 (δ = 196 ppm) > 6 (δ = 135 ppm) > 3 (δ = –30.9 ppm). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Formation of platinum–carbon σ-bonded complexes from co-ordinated and unco-ordinated olefins and acetylenes

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The Transition Metal Coordination Chemistry of Hemilabile Ligands

The Transition Metal Coordination Chemistry of Hemilabile Ligands

ChemInform Abstract: BLDG. VON KOMPLEXEN MIT EINER PT‐C‐SIGMA‐BINDUNG AUS KOORDINIERTEN UND NICHT‐KOORDINIERTEN OLEFINEN UND ACETYLENEN

Tris(dibenzo[a,d]cycloheptenyl)phosphane: A Bulky Monodentate or Tetrapodal Ligand

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