Reversible N−N Coupling of NO Ligands on Dinuclear Ruthenium Complexes and Subsequent N<sub>2</sub>O Evolution:  Relevance to Nitric Oxide Reductase

Arikawa, Yasuhiro; Asayama, Taiki; Moriguchi, Yusuke; Agari, Shoko; Onishi, Masayoshi

doi:10.1021/ja0763504

Cited by 68 publications

(95 citation statements)

References 18 publications

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“…96 DFT calculations (B3LYP level of theory using a LANL2DZ basis set for Ru) revealed that the highest occupied molecular orbital (HOMO) in this complex is primarily localized on the 18 N-N bond. 95 Significantly, the hyponitrite ligand in this complex is essentially identical to the (NO) 2 dimers proposed to form on metal surfaces during catalytic NO reduction. 22 Scheme 10.…”

Section: Scheme 2 Synthesis Of Trans-hyponitrous Acidmentioning

confidence: 60%

Understanding the Role of Hyponitrite in Nitric Oxide Reduction

Wright

Hayton

2015

Inorg. Chem.

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Herein, we review the preparation and coordination chemistry of the cis and trans isomers of hyponitrite, [N 2 O 2 ] 2-. Hyponitrite is known to bind to metals via a variety of bonding modes. In fact, at least eight different bonding modes have been observed, which is remarkable for such a simple ligand. More importantly, it is apparent that the cis isomer of hyponitrite is more reactive than the trans isomer, as the barrier of N 2 O elimination from cis-hyponitrite is lower than that of trans-hyponitrite. This observation may have important mechanistic implications for both heterogeneous NO x reduction catalysts and NO Reductase. However, our understanding of the hyponitrite ligand has been limited by the lack of a general route to this fragment, and most instances of its formation have been serendipitous.3

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Section: Scheme 2 Synthesis Of Trans-hyponitrous Acidmentioning

confidence: 60%

Understanding the Role of Hyponitrite in Nitric Oxide Reduction

Wright

Hayton

2015

Inorg. Chem.

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“…Ruthenium complexes bearing bis(pyrazolyl)borate (Bp) and tris(pyrazolyl)borate (Tp) ligands have attracted considerable research attentions [24][25][26][27]. However, only a limited number of ruthenium nitrosyl complexes with polypyrazolyborate ligands have been reported [28][29][30][31][32][33][34][35]. Onishi et al have reported the preparation and novel reactivities of the ruthenium nitrosyls bearing Tp ligand and their alkynyl derivatives [28][29][30][31][32][33][34][35].…”

Section: Introductionmentioning

confidence: 99%

“…However, only a limited number of ruthenium nitrosyl complexes with polypyrazolyborate ligands have been reported [28][29][30][31][32][33][34][35]. Onishi et al have reported the preparation and novel reactivities of the ruthenium nitrosyls bearing Tp ligand and their alkynyl derivatives [28][29][30][31][32][33][34][35]. Polypyrazolylmethanes, such as bis(3,5-dimethyl-1-pyrazolylmethane) (Bpm * ) and tris(1-pyrazolyl)methane (Tpm), are the neutral analogues of the Bp and Tp ligands [36,37], which are isosteric and isoelectronic with the anionic polypyrazolyborates.…”

Section: Introductionmentioning

confidence: 99%

Preparation, characterization, and catalytic properties of ruthenium nitrosyl complexes with polypyrazolylmethane ligands

Cheng

Sun

et al. 2008

Journal of Organometallic Chemistry

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“…These results are fully consistent with experimental observations. 44,45 3.3. Proton-Assisted Mechanisms.…”

Section: Geometric and Electronic Structures Of Dinitrosylmentioning

confidence: 99%

“…Very recently, we have shown that protons can play a significant role in the decomposition of NO (2NO → N 2 + O 2 ) catalyzed by a copper ion-exchanged zeolite Cu-ZSM-5, where N 2 O is one of the important intermediates in the catalytic cycle. 43 Arikawa and co-workers 44,45 recently synthesized a dinuclear ruthenium complex [(TpRu) 2 …”

Section: ■ Introductionmentioning

confidence: 99%

Proton-Assisted Mechanism of NO Reduction on a Dinuclear Ruthenium Complex

et al. 2015

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Density-functional-theory (DFT) calculations are performed for the proposal of a plausible mechanism on the reduction of NO to N2O by a dinuclear ruthenium complex, reported by Arikawa and co-workers [J. Am. Chem. Soc. 2007, 129, 14160]. On the basis of the experimental fact that the reduction proceeds under strongly acidic conditions, the role of protons in the mechanistic pathways is investigated with model complexes, where one or two NO ligands are protonated. The reaction mechanism of the NO reduction is partitioned into three steps: reorientation of N2O2 (cis-NO dimer), O-N bond cleavage, and N2O elimination. A key finding is that the protonation of the NO ligand(s) significantly reduces the activation barrier in the rate-determining reorientation step. The activation energy of 43.1 kcal/mol calculated for the proton-free model is reduced to 30.2 and 17.6 kcal/mol for the mono- and diprotonated models, respectively. The protonation induces the electron transfer from the Ru(II)Ru(II) core to the O═N-N═O moiety to give a Ru(III)Ru(III) core and a hyponitrite (O-N═N-O)(2-) species. The formation of the hyponitrite species provides an alternative pathway for the N2O2 reorientation, resulting in the lower activation energies in the presence of proton(s). The protonation also has a marginal effect on the O-N bond cleavage and the N2O elimination steps. Our calculations reveal a remarkable role of protons in the NO reduction via N2O formation and provide new insights into the mechanism of NO reduction catalyzed by metalloenzymes such as nitric oxide reductase (NOR) that contains a diiron active site.

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Reversible N−N Coupling of NO Ligands on Dinuclear Ruthenium Complexes and Subsequent N₂O Evolution: Relevance to Nitric Oxide Reductase

Abstract: Contents Experimental ProceduresTable S1.Crystallographic data for 2b•0.5(CH 2 ClCH 2 Cl) and 2c•C 6 H 5 Me

Cited by 68 publications

References 18 publications

Understanding the Role of Hyponitrite in Nitric Oxide Reduction

Understanding the Role of Hyponitrite in Nitric Oxide Reduction

Preparation, characterization, and catalytic properties of ruthenium nitrosyl complexes with polypyrazolylmethane ligands

Proton-Assisted Mechanism of NO Reduction on a Dinuclear Ruthenium Complex

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Reversible N−N Coupling of NO Ligands on Dinuclear Ruthenium Complexes and Subsequent N2O Evolution: Relevance to Nitric Oxide Reductase

Abstract: Contents Experimental ProceduresTable S1.Crystallographic data for 2b•0.5(CH 2 ClCH 2 Cl) and 2c•C 6 H 5 Me

Cited by 68 publications

References 18 publications

Understanding the Role of Hyponitrite in Nitric Oxide Reduction

Understanding the Role of Hyponitrite in Nitric Oxide Reduction

Preparation, characterization, and catalytic properties of ruthenium nitrosyl complexes with polypyrazolylmethane ligands

Proton-Assisted Mechanism of NO Reduction on a Dinuclear Ruthenium Complex

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Reversible N−N Coupling of NO Ligands on Dinuclear Ruthenium Complexes and Subsequent N₂O Evolution: Relevance to Nitric Oxide Reductase