Selective O-atom transfer from nitrous oxide to hydride and aryl ligands of bis(pentamethylcyclopentadienyl)hafnium derivatives

Vaughan, G.; Rupert, Peter B.; Hillhouse, Gregory L.

doi:10.1021/ja00252a047

Cited by 84 publications

(62 citation statements)

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“…The reduction of N 2 O is a thermodynamically favorable reaction with DG & -104.6 kJ mol -1 but its thermodecomposition is kinetically inert owing to the activation barrier of approximately 250 kJ mol -1 , which is consistent with a spin-forbidden process [21,71]. Although N 2 O is a weak ligand for metals, because it is a weak r-donor and weak p-acceptor molecule, several complexes of transition metals are able to bind and activate N 2 O [72,73].…”

Section: Activation Of the Cuz Centermentioning

confidence: 75%

The tetranuclear copper active site of nitrous oxide reductase: the CuZ center

et al. 2011

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This review focuses on the novel CuZ center of nitrous oxide reductase, an important enzyme owing to the environmental significance of the reaction it catalyzes, reduction of nitrous oxide, and the unusual nature of its catalytic center, named CuZ. The structure of the CuZ center, the unique tetranuclear copper center found in this enzyme, opened a novel area of research in metallobiochemistry. In the last decade, there has been progress in defining the structure of the CuZ center, characterizing the mechanism of nitrous oxide reduction, and identifying intermediates of this reaction. In addition, the determination of the structure of the CuZ center allowed a structural interpretation of the spectroscopic data, which was supported by theoretical calculations. The current knowledge of the structure, function, and spectroscopic characterization of the CuZ center is described here. We would like to stress that although many questions have been answered, the CuZ center remains a scientific challenge, with many hypotheses still being formed.

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Section: Activation Of the Cuz Centermentioning

confidence: 75%

The tetranuclear copper active site of nitrous oxide reductase: the CuZ center

et al. 2011

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“…[3] Reduction of N 2 O in homogenous systems normally requires transition metals, such as Ti, V, Ni, Zr, Ru, Hf, [4][5][6][7][8][9] as activation centers, where the required two electrons are either derived from the metal centers, which results in terminal [10,11] or bridged [4] metal-oxide products, or from the ligands through insertion of the oxygen atom into the metal-ligand bond. [5][6][7]12] To date, none of the reported metal/N 2 O complexes has been structurally determined crystallographically. The N 2 O unit in the [(NH 3 ) 5 Ru(N 2 O)] 2+ complex has been found from spectroscopy to coordinate to the ruthenium atom in a linear end-on mode by its terminal nitrogen atom.…”

Section: Introductionmentioning

confidence: 99%

N₂O Reduction by the μ₄‐Sulfide‐Bridged Tetranuclear Cu_Z Cluster Active Site

et al. 2004

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Nitrous oxide (N2O) reduction is a chemical challenge both in the selective oxidation of organic substrates by N2O and in the removal of N2O as a green-house gas. The reduction of N2O is thermodynamically favorable but kinetically inert, and requires activating transition-metal centers. In biological systems, N2O reduction is the last step in the denitrification process of the bacterial nitrogen cycle and is accomplished by the enzyme nitrous oxide reductase, whose active site consists of a micro4-sulfide-bridged tetranuclear CuZ cluster which has many unusual spectroscopic features. Recent studies have developed a detailed electronic-structure description of the resting CuZ cluster, determined its catalytically relevant state, and provided insight into the role of this tetranuclear copper cluster in N2O activation and reduction.

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“…6 Other Possible N 2 O Activation Modes. As discussed above, the most favorable mode for activation of N 2 O involves a direct attack on the terminal nitrogen from one of the Ru-H bonds via TS (1)(2)(3)(4)(5) . There is also a possibility that a dissociative mechanism operates in which one of the Ru-P bonds dissociates Scheme 3 Scheme 4 Figure 1.…”

Section: Methodsmentioning

confidence: 99%

“…The results seem unexpected because hydride attack on the LUMO of N 2 O should preferentially occur at the central N, as is evident in Figure 6. Clearly, the high barrier for this mode can also be attributed to the formation of a species that has a formally minus charge on the dangling (terminal) nitrogen (see TS (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19) and the intermediate 19 in eq 4 of Scheme 5).…”

Section: Methodsmentioning

confidence: 99%

Theoretical Studies on O-Insertion Reactions of Nitrous Oxide with Ruthenium Hydride Complexes

Jia

Lin

2008

Organometallics

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DFT calculations have been carried out to study the mechanism of the N2O O-insertion into the Ru−H bonds of ruthenium hydride complexes (dmpe)2Ru(H)(X) (X = OH, H). The reaction pathways for the formation of the monoinsertion product (dmpe)2Ru(H)(OH) and the bis(hydroxo) complex (dmpe)2Ru(OH)(OH), which were obtained directly from the reactions of N2O with the ruthenium hydride complexes, have been investigated in detail. Focus has been made to understand how the kinetically inert N2O is activated by the hydride complexes. It is found that N2O is activated through the hydride ligand nucleophilically attacking the terminal nitrogen of N2O followed by coordination of the activated N2O via the O-end.

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Selective O-atom transfer from nitrous oxide to hydride and aryl ligands of bis(pentamethylcyclopentadienyl)hafnium derivatives

Cited by 84 publications

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The tetranuclear copper active site of nitrous oxide reductase: the CuZ center

The tetranuclear copper active site of nitrous oxide reductase: the CuZ center

N₂O Reduction by the μ₄‐Sulfide‐Bridged Tetranuclear Cu_Z Cluster Active Site

Theoretical Studies on O-Insertion Reactions of Nitrous Oxide with Ruthenium Hydride Complexes

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Selective O-atom transfer from nitrous oxide to hydride and aryl ligands of bis(pentamethylcyclopentadienyl)hafnium derivatives

Cited by 84 publications

References 0 publications

The tetranuclear copper active site of nitrous oxide reductase: the CuZ center

The tetranuclear copper active site of nitrous oxide reductase: the CuZ center

N2O Reduction by the μ4‐Sulfide‐Bridged Tetranuclear CuZ Cluster Active Site

Theoretical Studies on O-Insertion Reactions of Nitrous Oxide with Ruthenium Hydride Complexes

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N₂O Reduction by the μ₄‐Sulfide‐Bridged Tetranuclear Cu_Z Cluster Active Site