212915-90-7Relevant academic research and scientific papers
Photochemical displacement of co-ordinated ethene from [Rh(η5-C5H5)(PPh3)(C 2H4)]
Heaton, Stephen N.,Partridge, Martin G.,Perutz, Robin N.,Parsons, Simon J.,Zimmermann, Frank
, p. 2515 - 2520 (1998)
The rhodium (triphenylphosphine)(ethene) complex [Rh(η5-C5H5)(PPh3)(C 2H4)], was synthesized by reaction of [{Rh(C2H4)2Cl}2] with triphenylphosphine and thallium cyclopentadienide. Like in [Rh(η5-C5H5)(PMe3)(C 2H4)], the co-ordinated ethene ligand may be displaced photochemically. Photoreaction of [Rh(η5-C5H5)(PPh3)(C 2H4)] with SiR3H (R = Pri or Et) and hexafluorobenzene yielded [Rh(η5-C5H5)(PPh3)(SiR 3)H] and [Rh(η5-C5H5)(PPh3)-(η 2-C6F6)], respectively. Oxidative addition of the C-H bonds of partially fluorinated arenes, C6F5H and 1,3-C6F2H4, was demonstrated by NMR spectroscopy to result in formation of [Rh(η5-C5H5)(PPh3)(R)H] (R = C6F5 or 2,6-C6F2H3). Oxidative addition of benzene may be detected following photolysis in benzene-thf mixtures at 233 K, but the product decomposes on warming. The molecular structure of [Rh(η5-C5H5)(PPh3)(SiPr i3)H] has been determined crystallographically. The disorder of the isopropyl groups was modelled with two orientations of the SiPri3 with equal occupancies. The Rh-Si bond length is 2.386(2) A, the first example of measurement of such a distance at cyclopentadienyl rhodium(III).
