Synthesis and Crystal Structure of a Peroxo‐Bridged Binuclear Rhodium (III) Complex and its Superoxo‐Bridged Analogue
1984; Wiley; Volume: 67; Issue: 8 Linguagem: Inglês
10.1002/hlca.19840670825
ISSN1522-2675
AutoresJ. Springborg, Margareta Zehnder,
Tópico(s)Asymmetric Hydrogenation and Catalysis
ResumoAbstract The reaction of the ammonia diol [(NH 3 ) 4 Rh(OH) 2 Rh(NH 3 ) 4 ] 4+ with H 2 O 2 Yields among other products a peroxo‐bridged dimeric species [(NH 3 ) 4 Rh(O 2 )(OH)Rh(NH 3 ) 3 (H 2 O)](CIO 4 ) 3 . Its structure was determined by single‐crystal X‐ray diffraction. The crystals are monoclinic with space group P 2 1 / n and lattice constants a =12.269 (5) Å, b =10.769(4) Å, c =15.964(4) Å, β=107.17(3)°. The dihedral angle of the RhOORh group in the bimetallic ring deviates by 62δ from planarity. The peroxo‐bridged complex was found to disproportionate in 1 M HCIO 4 and a red superoxo‐bridged complex. [(NH 3 ) 4 Rh(O 2 )(OH)Rh(NH 3 ) 3 (H 2 O)](NO 3 ) 4 , was isolated. Its structure was solved by single‐crystal X‐ray diffraction. The crystals are orthorhombic with space group Pna 2 , and lattice constants a =14.997(5) Å, b =11.952(4) Å, C=10.489(4) Å. The dihedral angle off the RhOORh group deviates by 7δ from planarity.
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