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- W2152079043 abstract "Abstract The tetradendate phosphane tris(5 H ‐dibenzo[ a , d ]cyclohepten‐5‐yl)phosphane (trop 3 P, 1 ) was synthesized from tris(trimethylsilyl)phosphane and 5‐chloro‐5 H ‐dibenzo[ a , d ]cycloheptene. Sulfurization of 1 with elemental sulfur led to trop 3 P=S. Complexes of 1 with Ag I , Au I , Rh I , Ir I , and Pd II were prepared. The structures of trop 3 P ( 1 ), trop 3 P=S ( 2 ), [AgCl(trop 3 P)] ( 3 ), [Au(trop 3 P)(MeCN)]PF 6 ( 5 ), [RhCl(trop 3 P)] ( 6 ) and [Pd(trop 3 P)(H 2 O)](OTf) 2 ( 9 ) were determined by X‐ray diffraction studies. In the coinage metal complexes, 1 serves as monodentate extremely bulky κ 1 ‐phosphane ligand (cone angle ca. 250°). In the Rh I , Ir I , and Pd II 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 31 P resonances. This property correlates inversely with the metal to olefin backbonding (M→C=C trop ) and δ ( 31 P) decreases with increasing M→C=C trop 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)" @default.
- W2152079043 created "2016-06-24" @default.
- W2152079043 creator A5017117840 @default.
- W2152079043 creator A5063987926 @default.
- W2152079043 creator A5091794897 @default.
- W2152079043 date "2007-06-01" @default.
- W2152079043 modified "2023-09-24" @default.
- W2152079043 title "Tris(dibenzo[ <i>a</i> , <i>d</i> ]cycloheptenyl)phosphane: A Bulky Monodentate or Tetrapodal Ligand" @default.
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