Nitrosyls and Thionitrosyls

J. R. Dethlefsen, A. Dossing, and E. D. Hedegard, Electron paramagnetic resonance studies of nitrosyl and thionitrosyl and density functional theory studies of nitride, nitrosyl, thionitrosyl, and selenoni-trosyl complexes of chromium, Inorg. Chem., 49 (2010) 8769-8778. 

Thermolysis of (LH)2[RuCl5(NO)] (L = benzimidazole, imidazole, 5-nitrobenzimidazole, benzo-triazole, py) leads to the initial formation of [RuC NOJL]- with subsequent reaction to afford [RuCl3(NO)L2].M6 When solutions of RuCl with NaNCS in pyridine are refluxed for three days, a product formulated as [Ru(NCS)2py4] can be isolated.667 Nitrosyl and thionitrosyl complexes containing heterocycles with arsine or phosphine ligands have been reported.668... 

The EPR spectra of low-spin 4d5 Tc(II) nitrosyl and thionitrosyl complexes have been examined in detail and the results, reviewed (39-41). 

Dinitrogen, Phosphine, Phosphite, and Related Complexes Complexes with Nitrogen Ligands Nitrosyl and Thionitrosyl Complexes Technetium(II)... 

Complexes with Dioximes, Schiff Bases, and Other Nitrogen Ligands Complexes with Monodentate Phosphines and Related Ligands Complexes with Bidentate Phosphine, Arsine, and Related Ligands Complexes with Sulfur Ligands Nitrosyl and Thionitrosyl Complexes VII. Technetium(IV)... 

NMR for some dinitrogen compounds are presented in Table 11 while data for nitrosyl species appear in Table 10. These data suggest the following overall shielding order CO>P(Alk)3>P(Ar)3>N2>NJ s NCR > NO > N=NR > N-NRI . Clearly, all the terms in the Ramsey expression are important here. Few new data for nitrosyl and thionitrosyl compounds have been reported since the last review. ... 

Scheme 3 Comparison of bond lengths in nitrido, nitrosyl and thionitrosyl molybdemnn complexes...

The condensation chemistry of 2, and is quite similar in that in all systems fragment ions wTll react with the parent neutral to form more complex ions. In the CpMn(C0)3, 1, system, these condensation reactions stop after the formation oT tertiary ions. In contrast, in the chromium nitrosyl,, and thionitrosyl, systems, the tertiary ions are reactive. 

---