Reactivity of the Re-NO centre: Proton induced oxidation of Re(NO)2+ to Re(NO)3+. Synthesis and characterisation of some Re(II) thiocyanato-halogenonitrosyl complexes |
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Authors: | Ramgopal Bhattacharyya Anup K Dasmahapatra and Partha S Roy |
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Institution: | (1) Department of Chemistry, Jadavpur University, 700032 Calcutta, India |
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Abstract: | The Re(NO)2+ moiety as Re(NO)(NCS)3H2O]− or Re(NO)(NCS)2(L-L)H2O]· L-L = phen (1,10-phenanthroline) or bipy (2,2′-bipyridine)] undergoes proton-induced oxidation reaction with HX (X =
Cl, Br) to produce a Re(NO)3+ moiety. The spectral and physico-chemical data suggest that the anionic complex is 5 coordinate and the neutral one is 6
coordinate with axial NO group and two NCS ligands intrans-equatorial positions. The complex, Re(NO)(NCS)2(phen)Br]·H2O shows complicated magnetic behaviour which is discussed in the paper. The ESR spectrum of this compound shows typical rhenium
hyperfines and <g>-tensor anisotropy compatible with the loss of axial symmetry. However, the spectrum of Re(NO)(NCS)2Br2]− quite reasonably shows axial symmetry, other features being grossly comparable to the L-L compounds. The anionic species
and the neutral L-L complex show irreversible one-electron oxidation waves at different voltages. This may correspond to a
conversion of Re(NO)3+ to Re(NO)4+ in both the cases. Interestingly enough, only the neutral complexes exhibit an irreversible reduction wave due probably to
a conversion of Re(NO)3+ to Re(NO)2+. |
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Keywords: | Reductive nitrosylation proton induced oxidation temperature-independent paramagnetism exchange inversion thiocyanato-halogenonitrosyls of rhenium |
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