1,4-Bis(4-nitrosophenyl)piperazine: novel bridging ligand in dinuclear complexes of rhodium(III) and iridium(III)

The synthesis, spectroscopic characterization and crystal structures of the first 1,4-bis(4-nitrosophenyl)piperazine (BNPP) (4) bridged dinuclear complexes of rhodium(III) and iridium(III) are presented. The reaction of the μ(2)-halogenido-bridged dimers [(η(5)-C(5)Me(5))IrX(2)](2) [X = Cl (5a), Br...

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Veröffentlicht in:Dalton transactions : an international journal of inorganic chemistry 2012-02, Vol.41 (7), p.2176-2186
Hauptverfasser: Wirth, Stefan, Barth, Florian, Lorenz, Ingo-Peter
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Sprache:eng
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Zusammenfassung:The synthesis, spectroscopic characterization and crystal structures of the first 1,4-bis(4-nitrosophenyl)piperazine (BNPP) (4) bridged dinuclear complexes of rhodium(III) and iridium(III) are presented. The reaction of the μ(2)-halogenido-bridged dimers [(η(5)-C(5)Me(5))IrX(2)](2) [X = Cl (5a), Br (5b), I (5c)] and [(η(5)- C(5)Me(5))RhCl(2)](2) (6a) with 4 yields the dinuclear complexes [(η(5)-C(5)Me(5))IrX(2)](2)-BNPP (7a-c) and [(η(5)-C(5)Me(5))RhCl(2)](2)-BNPP (8a). All new compounds were characterized by their NMR, IR and mass spectra. The X-ray structure analyses of the obtained half-sandwich complexes revealed a slightly distorted pseudo-octahedral configuration ("three-legged pianostool") for the metal(III) centers. The bridging BNPP ligand is σ-N coordinated by both nitroso groups and shows different conformations of the piperazine ring depending on the solvent used for crystallization. Moreover the crystal structures of 1,4-bis(4-nitrosophenyl)piperazine (4) and its precursor 1,4-diphenylpiperazine (3) are reported.
ISSN:1477-9226
1477-9234
DOI:10.1039/c1dt11696g