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Synthetic Models of Copper–Nitrosyl Species Proposed as Intermediates in Biological Denitrification

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Nitrosyl Complexes in Inorganic Chemistry, Biochemistry and Medicine II

Part of the book series: Structure and Bonding ((STRUCTURE,volume 154))

Abstract

Copper-containing nitrite reductase enzymes catalyze the reduction of nitrite to nitric oxide during denitrification, a key component of the global nitrogen cycle. Insights into the properties of proposed copper–nitrosyl intermediates have been obtained through studies of model complexes. Such complexes comprising both copper and nickel exhibit variable geometries and electronic structures that are influenced by the supporting ligands.

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Abbreviations

Ar:

Aryl

atm:

Atmosphere

Bpy:

2,2′-Bipyridyl

Bu:

Butyl

Cp:

Cyclopentadienyl

Cu-NiR:

Copper nitrite reductase enzyme

Cy:

Cyclohexyl

dmp:

2,9-Dimethyl-1,10-phenanthroline

ENDOR:

Electron-nuclear double resonance

EPR:

Electron paramagnetic resonance

equiv:

Equivalent(s)

ESI-MS:

Electrospray ionization mass spectrometry

Et:

Ethyl

h:

Hour(s)

His:

Histidine

Im:

Imidazole

iPr:

Isopropyl

IR:

Infrared spectroscopy

MCD:

Magnetic circular dichroism

Me:

Methyl

Mes:

Mesityl 2,4,6-trimethylphenyl (not methanesulfonyl)

min:

Minute(s)

mol:

Mole(s)

NMR:

Nuclear magnetic resonance

Ph:

Phenyl

py:

Pyridine

pz:

Pyrazolyl

rt:

Room temperature

s:

Second(s)

tBu:

tert-Butyl

THF:

Tetrahydrofuran

TMEDA:

N,N,N',N'-tetramethyl-1,2-ethylenediamine

Tol:

4-Methylphenyl

Tp:

Tris(pyrazolyl)hydroborate

UV–vis:

Ultraviolet–visible

XAS:

X-ray absorption spectroscopy

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Authors and Affiliations

  1. Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN, 55455, USA

    Debra J. Salmon & William B. Tolman

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  1. Debra J. Salmon
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  2. William B. Tolman
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Correspondence to William B. Tolman .

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  1. Inorganic Chemistry Laboratory, University of Oxford, Oxford, United Kingdom

    D. Michael P. Mingos

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Salmon, D.J., Tolman, W.B. (2013). Synthetic Models of Copper–Nitrosyl Species Proposed as Intermediates in Biological Denitrification. In: Mingos, D. (eds) Nitrosyl Complexes in Inorganic Chemistry, Biochemistry and Medicine II. Structure and Bonding, vol 154. Springer, Berlin, Heidelberg. https://doi.org/10.1007/430_2013_93

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