Synthesis, reactivity, and X-ray crystal structure of [Rh{C6H4N(O)O-2}(η-C5Me5)Cl]
- 1 January 1990
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 4,p. 1459-1462
- https://doi.org/10.1039/dt9900001459
Abstract
Reaction of [{Rh(η-C5Me5)Cl2}2] with [Hg(C6H4NO2-2)2](1/1) or [Hg(C6H4NO2-2)Cl](1/2) in the presence of an excess of [NMe4]Cl gives [[graphic omitted]-2}(η-C5Me5)Cl]. This compound reacts with AgClO4 giving solutions from which, after addition of the corresponding ligands, the cationic complexes [[graphic omitted]-2}(η-C5Me5)(PPh3)]ClO4, [[graphic omitted]-2}(η-C5Me5)(py)]ClO4(py = pyridine), [Rh(C6H4NO2-2)(η-C5Me5)(bipy)]ClO4(bipy = 2,2′-bipyridyl) can be obtained. The crystal structure of [[graphic omitted]-2}(η-C5Me5)Cl] has been determined by an X-ray diffraction study. Crystals are orthorhombic, space group Pbca, with a= 14.574 2(5), b= 14.917 8(6), c= 14.678 2(6)Å, and Z= 8. The molecule exhibits a pseudo-octahedral geometry around the rhodium atom with the C6H4(O)O-2 group acting as a chelating ligand, bonded to the metal through a carbon atom of the phenyl ring [Rh–C(1) 2.023(3)Å] and an oxygen atom of the nitro group [Rh–O(1) 2.142(3)Å]. The co-ordination of the nitro group causes a lengthening of the N–O(Rh) bond distance [N–O(1) 1.260(4)Å] compared with the unco-ordinated N–O bond length [1.224(4)Å]. Infrared data indicate that the aryl ligand co-ordinates in the same way in the complexes [[graphic omitted]-2}(η-C5Me5)(PPh3)]ClO4 and [[graphic omitted]-2}(η-C5Me5)(py)]ClO4 but it is unidentate in the compound [Rh(C6H4NO2-2)(η-C5Me5)(bipy)]ClO4.Keywords
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