ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The reaction of the meso-diol, Δ,Λ-[(en)2Rh(OH)2Rh(en)2]4+, with aqueous H2O2 and 1 equiv. of NaOH at 90° forms the μ-peroxo-μ-hydroxo-bridged species Δ,Λ-[(en)2Rh(O2,OH)Rh(en)2]3+ in a yield of ca. 50%. The compound was crystallized as perchlorate and trifluoromethanesulfonate salts. The structure of the latter salt was determined by single-crystal X-ray diffraction. The crystals are triclinic with space group P1 and lattice constants a = 11.895(5), b = 12.491(4), c = 13.053(5) Å, α = 103.98(3), β = 92.59(3), γ = 119.52(6)°. The distances of the metal centres to the bridging peroxo ligand are 1.999(8) and 1.983(6) Å. The O—O distance in the peroxo group is 1.521(14) Å, and the dihedral angle of the Rh—O—O—Rh unit deviates 65° from planarity. The peroxo complex reacts reversibly with acid, and spectrophotometric studies suggest that the reaction involves protonation of the peroxo bridge, with pKa = 2.70(2) at 25° in 1M NaClO4.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19860690124
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