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Title: Rapid reduction of nitric oxide to dinitrogen by zirconium(II): Kinetic studies on a reaction controlled by gas-liquid transport

Abstract

Nitric oxide reacts with Cp{sub 2}Zr(PMe{sub 3}){sub 2} (1; Cp = {eta}{sup 5}-C{sub 5}H{sub 5} in THF or toluene to yield dinitrogen and an oligomeric oxozirconocene species, [Cp{sub x}ZrO{sub y}]{sub n}. The reduction of NO occurs in two distinct steps: 1 reduces 2 equiv of NO to 1 equiv of N{sub 2}), and then 1 reduces N{sub 2}O to N{sub 2}. In each step, 1 is converted to a monomeric oxozirconocene species [Cp{sub 2}ZrO], which may be trapped by the addition of Me{sub 3}SiCl or Cp{sub 2}ZrMe{sub 2}, to form Cp{sub 2}Zr(OSiMe{sub 3})(Cl) and [Cp{sub 2}ZrMe]{sub 2}O, respectively. Kinetics for the reduction of NO by 1 were followed at low temperature (160 < T < 195 K) by monitoring the change in pressure of the system. Complete reaction was observed in less than 15 s, even at the lowest temperatures. The typical kinetic trace displayed two decay regimes, zero- and first-order, which were interpreted as the result of competing mass-transfer and chemical reaction processes. The kinetic results support a rate-limiting bimolecular reaction between NO and 1. The subsequent intermediates and mechanistic possibilities are discussed.

Authors:
;
Publication Date:
Research Org.:
Univ. of California, Berkeley (US)
OSTI Identifier:
20000127
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 121; Journal Issue: 36; Other Information: PBD: 15 Sep 1999; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; REDUCTION; ZIRCONIUM COMPLEXES; NITRIC OXIDE; NITROGEN; PHOSPHORUS COMPOUNDS; CHEMICAL REACTION KINETICS

Citation Formats

McNeill, K., and Bergman, R.G. Rapid reduction of nitric oxide to dinitrogen by zirconium(II): Kinetic studies on a reaction controlled by gas-liquid transport. United States: N. p., 1999. Web. doi:10.1021/ja983011p.
McNeill, K., & Bergman, R.G. Rapid reduction of nitric oxide to dinitrogen by zirconium(II): Kinetic studies on a reaction controlled by gas-liquid transport. United States. doi:10.1021/ja983011p.
McNeill, K., and Bergman, R.G. Wed . "Rapid reduction of nitric oxide to dinitrogen by zirconium(II): Kinetic studies on a reaction controlled by gas-liquid transport". United States. doi:10.1021/ja983011p.
@article{osti_20000127,
title = {Rapid reduction of nitric oxide to dinitrogen by zirconium(II): Kinetic studies on a reaction controlled by gas-liquid transport},
author = {McNeill, K. and Bergman, R.G.},
abstractNote = {Nitric oxide reacts with Cp{sub 2}Zr(PMe{sub 3}){sub 2} (1; Cp = {eta}{sup 5}-C{sub 5}H{sub 5} in THF or toluene to yield dinitrogen and an oligomeric oxozirconocene species, [Cp{sub x}ZrO{sub y}]{sub n}. The reduction of NO occurs in two distinct steps: 1 reduces 2 equiv of NO to 1 equiv of N{sub 2}), and then 1 reduces N{sub 2}O to N{sub 2}. In each step, 1 is converted to a monomeric oxozirconocene species [Cp{sub 2}ZrO], which may be trapped by the addition of Me{sub 3}SiCl or Cp{sub 2}ZrMe{sub 2}, to form Cp{sub 2}Zr(OSiMe{sub 3})(Cl) and [Cp{sub 2}ZrMe]{sub 2}O, respectively. Kinetics for the reduction of NO by 1 were followed at low temperature (160 < T < 195 K) by monitoring the change in pressure of the system. Complete reaction was observed in less than 15 s, even at the lowest temperatures. The typical kinetic trace displayed two decay regimes, zero- and first-order, which were interpreted as the result of competing mass-transfer and chemical reaction processes. The kinetic results support a rate-limiting bimolecular reaction between NO and 1. The subsequent intermediates and mechanistic possibilities are discussed.},
doi = {10.1021/ja983011p},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 36,
volume = 121,
place = {United States},
year = {1999},
month = {9}
}