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Nitric oxide monooxygenation (NOM) reaction of cobalt-nitrosyl {Co(NO)}⁸ to Co^II-nitrito {Co^II(NO₂ ^-)}: base induced hydrogen gas (H₂) evolution.

ABSTRACT: Here, we report the nitric oxide monooxygenation (NOM) reactions of a Co^III-nitrosyl complex (1, {Co-NO}⁸) in the presence of mono-oxygen reactive species, i.e., a base (OH^-, tetrabutylammonium hydroxide (TBAOH) or NaOH/15-crown-5), an oxide (O^2- or Na₂O/15-crown-5) and water (H₂O). The reaction of 1 with OH^- produces a Co^II-nitrito complex {3, (Co^II-NO₂ ^-)} and hydrogen gas (H₂), via the formation of a putative N-bound Co-nitrous acid intermediate (2, {Co-NOOH}⁺). The homolytic cleavage of the O-H bond of proposed [Co-NOOH]⁺ releases H₂ via a presumed Co^III-H intermediate. In another reaction, 1 generates Co^II-NO₂ ^- when reacted with O^2- via an expected Co^I-nitro (4) intermediate. However, complex 1 is found to be unreactive towards H₂O. Mechanistic investigations using ¹⁵N-labeled-¹⁵NO and ²H-labeled-NaO²H (NaOD) evidently revealed that the N-atom in Co^II-NO₂ ^- and the H-atom in H₂ gas are derived from the nitrosyl ligand and OH^- moiety, respectively.

SUBMITTER: Das S

PROVIDER: S-EPMC8159239 | biostudies-literature | 2020 Apr

REPOSITORIES: biostudies-literature

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Nitric oxide monooxygenation (NOM) reaction of cobalt-nitrosyl {Co(NO)}8 to CoII-nitrito {CoII(NO2 -)}: base induced hydrogen gas (H2) evolution.

Das Sandip S Kulbir Ghosh Somnath S Chandra Sahoo Subash S Kumar Pankaj P

Chemical science 20200424 19

Here, we report the nitric oxide monooxygenation (NOM) reactions of a CoIII-nitrosyl complex (1, {Co-NO}8) in the presence of mono-oxygen reactive species, i.e., a base (OH-, tetrabutylammonium hydroxide (TBAOH) or NaOH/15-crown-5), an oxide (O2- or Na2O/15-crown-5) and water (H2O). The reaction of 1 with OH- produces a CoII-nitrito complex {3, (CoII-NO2 ...[more]

PMID: 34122960

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Project description:Neutral {CpFeII(CO)2[SnII(Pc•3-)]} {Cp is cyclopentadienyl (1, 2) or Cp* is pentamethylcyclopentadienyl (3); Pc: phthalocyanine}, {Cp*FeII(CO)2[SnII(Nc•3-)]} (4, Nc: naphthalocyanine), and {CpFeII(CO)2[SnII(TPP•3-)]} (5, TPP: tetraphenylporphyrin) complexes in which CpFeII(CO)2 fragments (Cp: Cp or Cp*) are coordinated to SnII(macrocycle•3-) have been obtained. The product complexes were obtained at the reaction of charge transfer from CpFeI(CO)2 (Cp: Cp or Cp*) to [SnII(macrocycle2-)] to form the diamagnetic FeII and paramagnetic radical trianionic macrocycles. As a result, these formally neutral complexes contain S = 1/2 spins delocalized over the macrocycles. This provides alternation of the C-Nimine or C-Cmeso bonds in the macrocycles, the appearance of new bands in the near-infrared spectra of the complexes, and blue shift of both Soret and Q-bands. The {CpFeII(CO)2SnII(macrocycle•3-)} units (Cp: Cp or Cp*, macrocycle: Pc or Nc) form closely packed π-stacking dimers in 1 and 3 or one-dimensional chains in 2 and 4 with effective π-π interaction between the macrocycles. Such packing allows strong antiferromagnetic coupling between S = 1/2 spins. Magnetic interaction can be described well by the Heisenberg model for the isolated dimers in 1 and 3 with exchange interaction J/k B = -78 and -85 K, respectively. Magnetic behavior of 2 and 4 is described well by the model that includes contributions from an antiferromagnetically coupled S = 1/2 dimer (J intra) and a Heisenberg S = 1/2 chain with alternating antiferromagnetic spin exchange between the neighbors (J inter). Compound 2 demonstrates large intradimer interaction of J intra/k B = -54 K and essentially weaker interdimer exchange interactions of J inter/k B = -6 K, whereas compound 4 shows strong magnetic coupling of spins within the dimers (J intra/k B = -170 K) as well as between the dimers (J inter/k B = -40 K). Compound {CpFeII(CO)2[SnII(TPP•3-)]} (5) shows no π-π interactions between the porphyrin macrocycles, and magnetic coupling is weak in this case (Weiss temperature is -5 K). Preparation of a similar complex with indium(III) chloride phthalocyanine yields {CpFe(CO)2[In(Pc2-)]} (6). In this complex, indium(III) atoms are reduced instead of the phthalocyanine macrocycles that explains electron paramagnetic resonance silence of 6 in the 4-295 K range.

Dataset Information

Nitric oxide monooxygenation (NOM) reaction of cobalt-nitrosyl {Co(NO)}⁸ to Co^II-nitrito {Co^II(NO₂ ^-)}: base induced hydrogen gas (H₂) evolution.

Publications

Nitric oxide monooxygenation (NOM) reaction of cobalt-nitrosyl {Co(NO)}<sup>8</sup> to Co<sup>II</sup>-nitrito {Co<sup>II</sup>(NO<sub>2</sub> <sup>-</sup>)}: base induced hydrogen gas (H<sub>2</sub>) evolution.

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