75812-19-0Relevant academic research and scientific papers
Reduction-Oxidation Properties of Organotransition-metal Complexes. Part 9. Silver(I) Adducts of Cyclic Polyeneone Complexes, the X-Ray Crystal Structure of 5-C5Ph4OAg(OH2)>>2>2, and Comments on the Use of the Silver(I) Ion as a One-electron Oxidant
Baker, Paul K.,Broadley, Karen,Connelly, Neil G.,Kelly, Barbara A.,Kitchen, Maureen D.,Woodward, Peter
, p. 1710 - 1715 (2007/10/02)
The tetraphenylcyclopentadienone complexes 4-C5Ph4O)> and 5-C5H5)(η4-C5Ph4O)> (2) react with Ag to give dimeric oxygen-bonded silver adducts 5-C5Ph4OAg)>2>2 (3) and 5-C5H5)(η5-C5Ph4OAg)>2>2 (4).The X-ray crystal structure of (3; M = Fe, L = CO) confirms that the cation contains a central planar asymmetric Ag2O2 bridge (Ag-O 2.27 and 2.65 Angstroem) but there is a molecule of water co-ordinated to each Ag atom.The five-membered ring of the Fe(CO)3(C5Ph4O) moiety is best regarded as a substituted cyclopentadienyl although the carbon atom bearing the oxygen is significantly further from the iron atom (Fe-C, 2.31 Angstroem) than are the other four carbon atoms (Fe-C, 2.11 (mean) Angstroem>.There are also weak interactions between the silver atom and the two phenyl rings adjacent to the CO group in the C5 ring.The crystals were of poor quality, due to partial inclusion of molecules of CH2Cl2 the positions of which were not refined.This is reflected in the relatively poor R value and high standard deviations. The crystals are monoclinic, a = 13.293(7), b = 14.128(6), c = 19.805(14) Angstroem, β = 105.75(5) deg, space group P21/n.The structure was solved by heavy-atom methods and refined to R 0.115 for 2 847 reflections.The iron complexes (3) react with halide ions to regenerate (1), but form 4-C5Ph4O)> with halogens.Reaction of Ag with 6-tropone)> gives 7-C7H6(OH)>> via the decomposition of an adduct related to (3) and (4).A summary is given of the behaviour of AgI as a reagent in organometallic chemistry, and a brief comment made on its use as a one-electron oxidant.
