Reduction of nitrous oxide to dinitrogen by a mixed valenttricopper- disulfido cluster

Itslk Bar-Nahum; Aalo K. Gupta; Stefan M. Huber; Mehmed Z. Ertem; Christopher J. Cramer; William B. Tolman

doi:10.1021/ja808917k

Reduction of nitrous oxide to dinitrogen by a mixed valenttricopper- disulfido cluster

Itslk Bar-Nahum, Aalo K. Gupta, Stefan M. Huber, Mehmed Z. Ertem, Christopher J. Cramer, William B. Tolman

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

72 Scopus citations

Abstract

(Figure Presented) The greenhouse gas N ₂O is converted to N ₂ by a μ-sulfido-tetracopper active site in the enzyme nitrous oxide reductase (N ₂OR) via a process postulated to involve μ-1,3 coordination of N ₂O to two Cu(I) ions. In efforts to develop synthetic models of the site with which to test mechanistic hypotheses, we have prepared a localized mixed valent Cu(II)Cu(I) ₂ cluster bridged in a μ-η ²:η ¹:η ¹ fashion by disulfide, [L ₃Cu ₃(μ ₃-S ₂)]X ₂ (L = 1,4,7-trimethyltriazacyclononane, X = O ₃SCF ₃ ^- or SbF ₆ ^-). This cluster exhibits spectroscopic features superficially similar to those of the active site in N ₂OR and reacts with N ₂O to yield N ₂ in a reaction that models the function of the enzyme. Computations implicate a transition state structure that features μ-1,1-bridging of N ₂O via its O-atom to a [L ₂Cu ₂(μ-S ₂)] ⁺ fragment and provide chemical precedence for an alternative pathway for N ₂O reduction by N ₂OR.

Original language	English (US)
Pages (from-to)	2812-2814
Number of pages	3
Journal	Journal of the American Chemical Society
Volume	131
Issue number	8
DOIs	https://doi.org/10.1021/ja808917k
State	Published - Mar 4 2009

Access

10.1021/ja808917k

OpenUrl availability

Full text

Cite this

@article{4fd3906194374f65ad79deef6136aba9,

title = "Reduction of nitrous oxide to dinitrogen by a mixed valenttricopper- disulfido cluster",

abstract = "(Figure Presented) The greenhouse gas N 2O is converted to N 2 by a μ-sulfido-tetracopper active site in the enzyme nitrous oxide reductase (N 2OR) via a process postulated to involve μ-1,3 coordination of N 2O to two Cu(I) ions. In efforts to develop synthetic models of the site with which to test mechanistic hypotheses, we have prepared a localized mixed valent Cu(II)Cu(I) 2 cluster bridged in a μ-η 2:η 1:η 1 fashion by disulfide, [L 3Cu 3(μ 3-S 2)]X 2 (L = 1,4,7-trimethyltriazacyclononane, X = O 3SCF 3 - or SbF 6 -). This cluster exhibits spectroscopic features superficially similar to those of the active site in N 2OR and reacts with N 2O to yield N 2 in a reaction that models the function of the enzyme. Computations implicate a transition state structure that features μ-1,1-bridging of N 2O via its O-atom to a [L 2Cu 2(μ-S 2)] + fragment and provide chemical precedence for an alternative pathway for N 2O reduction by N 2OR.",

author = "Itslk Bar-Nahum and Gupta, {Aalo K.} and Huber, {Stefan M.} and Ertem, {Mehmed Z.} and Cramer, {Christopher J.} and Tolman, {William B.}",

year = "2009",

month = mar,

day = "4",

doi = "10.1021/ja808917k",

language = "English (US)",

volume = "131",

pages = "2812--2814",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "8",

}

TY - JOUR

T1 - Reduction of nitrous oxide to dinitrogen by a mixed valenttricopper- disulfido cluster

AU - Bar-Nahum, Itslk

AU - Gupta, Aalo K.

AU - Huber, Stefan M.

AU - Ertem, Mehmed Z.

AU - Cramer, Christopher J.

AU - Tolman, William B.

PY - 2009/3/4

Y1 - 2009/3/4

N2 - (Figure Presented) The greenhouse gas N 2O is converted to N 2 by a μ-sulfido-tetracopper active site in the enzyme nitrous oxide reductase (N 2OR) via a process postulated to involve μ-1,3 coordination of N 2O to two Cu(I) ions. In efforts to develop synthetic models of the site with which to test mechanistic hypotheses, we have prepared a localized mixed valent Cu(II)Cu(I) 2 cluster bridged in a μ-η 2:η 1:η 1 fashion by disulfide, [L 3Cu 3(μ 3-S 2)]X 2 (L = 1,4,7-trimethyltriazacyclononane, X = O 3SCF 3 - or SbF 6 -). This cluster exhibits spectroscopic features superficially similar to those of the active site in N 2OR and reacts with N 2O to yield N 2 in a reaction that models the function of the enzyme. Computations implicate a transition state structure that features μ-1,1-bridging of N 2O via its O-atom to a [L 2Cu 2(μ-S 2)] + fragment and provide chemical precedence for an alternative pathway for N 2O reduction by N 2OR.

AB - (Figure Presented) The greenhouse gas N 2O is converted to N 2 by a μ-sulfido-tetracopper active site in the enzyme nitrous oxide reductase (N 2OR) via a process postulated to involve μ-1,3 coordination of N 2O to two Cu(I) ions. In efforts to develop synthetic models of the site with which to test mechanistic hypotheses, we have prepared a localized mixed valent Cu(II)Cu(I) 2 cluster bridged in a μ-η 2:η 1:η 1 fashion by disulfide, [L 3Cu 3(μ 3-S 2)]X 2 (L = 1,4,7-trimethyltriazacyclononane, X = O 3SCF 3 - or SbF 6 -). This cluster exhibits spectroscopic features superficially similar to those of the active site in N 2OR and reacts with N 2O to yield N 2 in a reaction that models the function of the enzyme. Computations implicate a transition state structure that features μ-1,1-bridging of N 2O via its O-atom to a [L 2Cu 2(μ-S 2)] + fragment and provide chemical precedence for an alternative pathway for N 2O reduction by N 2OR.

UR - http://www.scopus.com/inward/record.url?scp=67749103820&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=67749103820&partnerID=8YFLogxK

U2 - 10.1021/ja808917k

DO - 10.1021/ja808917k

M3 - Article

C2 - 19206272

AN - SCOPUS:67749103820

SN - 0002-7863

VL - 131

SP - 2812

EP - 2814

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 8

ER -

Reduction of nitrous oxide to dinitrogen by a mixed valenttricopper- disulfido cluster

Abstract

Access

OpenUrl availability

Other files and links

Fingerprint

Cite this