Synthesis and Crystal Structure of meso-Δ,Λ-μ-Peroxo-μ-hydroxobis[bis(ethylenediamine)rhodium(III)]trifluoromethane Sulfonate
✍ Scribed by Johan Springborg; Margareta Zehnder
- Publisher
- John Wiley and Sons
- Year
- 1986
- Tongue
- German
- Weight
- 581 KB
- Volume
- 69
- Category
- Article
- ISSN
- 0018-019X
No coin nor oath required. For personal study only.
✦ Synopsis
Dedicated to Prof. Dr. Siluio Fullub on the occasion of his 60th birthday (23.1X.85) The reaction of the meso-diol, A,A-[(en),Rh(OH)2Rh(en)2]4+, with aqueous H,O, and 1 equiv. of NaOH at YO" forms the pperoxo-p-hydroxo-bridged species ~l,A-[(en),Rh(O,,OH)Rh(en)~]~+ in a yield of cu. 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 P i and lattice constants u = 11.895( 5), b = 12.491(4), c = 13.053(5) A, a = 103.98(3), fi = Y2.59(3), y = 119.52( 6)". The distances of the metal centres to the bridging peroxo ligand are 1.999(8) and 1.983(6) A. The 0-0 distance in the peroxo group is 1.521(14) A, and the dihedral angle of the Rh-0-0-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 pK, = 2.70(2) at 25" in I M NaCIO,.