Reductive nitrosylation of nickel(ii) complex by nitric oxide followed by nitrous oxide release

Abstract

Ni(ii) complex of ligand ( = bis(2-ethyl-4-methylimidazol-5-yl)methane) in methanol solution reacts with an equivalent amount of NO resulting in a corresponding Ni(i) complex. Adding further NO equivalent affords a Ni(i)-nitrosyl intermediate with the {NiNO}(10) configuration. This nitrosyl intermediate upon subsequent reaction with additional NO results in the release of N2O and formation of a Ni(ii)-nitrito complex. Crystallographic characterization of the nitrito complex revealed a symmetric η(2)-O,O-nitrito bonding to the metal ion. This study demonstrates the reductive nitrosylation of a Ni(ii) center followed by N2O release in the presence of excess NO.

Reaction of a Co(III)-Peroxo Complex and NO: Formation of a Putative Peroxynitrite Intermediate

“…The ligand L ( L = bis­(2-ethyl-4-methylimidazol-5-yl)­methane) was synthesized by following the earlier reported procedure . The Co­(II) complex 1 , [Co II (L) 2 ]­Cl 2 , was prepared by stirring a mixture of cobalt­(II) chloride hexahydrate with 2 equiv of the ligand in methanol (Experimental Section).…”

“…The ligand was prepared from the reaction of 2-ethyl-4-methyl imidazole (2.2 g; 20 mM) and formaldehyde (0.45 g; 15 mM) using the protocol reported earlier . Yield: 1.97 g (ca.…”

NO˙ disproportionation by a {RhNO}9pincer-type complex

“…7 This bond activation reactivity reflects the ability of the nitrosyl ligand to act as an electron reservoir. disproportionation by metal complexes to give N 2 O and metal nitrite complexes, 7,[9][10][11][12][13][14] although in one case dinitrogen (N 2 ) was reported as the reduced product. 7 This disproportionation reaction (eq.…”

“…The band at 1640 cm-1 corresponds to the nitrite complex Rh(PCP)( 14 NO)(NO 2 ) (2-14 NO) (Scheme 1), while the band at 1612 cm -1 is attributed to its 2-15 NO counterpart. On the other hand, the peaks at 2219, 2196, 2173 and 2150 cm -1 , that increased upon the incremental addition of 14 NO(Figure 3, inset), are assigned to14 N 2 O, 14 N 15 NO, 15 N 14 NO and 15 N 2 O, respectively 21. The binding of NO • vacuum and is not displaced by trimethylphosphine), so the complete scrambling of labels in the formation of N 2 O, could be explained as the result of the formation of a dinitrosyl complex in equilibrium with the mononitrosyl, as shown in Scheme 3.…”

Reduction of Nitrogen Oxides by Hydrogen with Rhodium(I)–Platinum(II) Olefin Complexes as Catalysts

“…[17] To the best of our knowledge,n oh omogeneous catalytic system has been reported for the catalytic reduction of NO or NO 2 with hydrogen. Only stoichiometric reactions with iron, [18] nickel, [19] copper, [20] or ruthenium complexes were reported recently. [21] Nature has developed as et of enzymes that can catalyze the reduction of N 2 Oand NO.…”