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A multi-iron system capable of rapid N2 formation and N2 cleavage.

MacLeod KC, Vinyard DJ, Holland PL - J. Am. Chem. Soc. (2014)

Bottom Line: Surprisingly, these mild reagents generate high yields of iron(I) products from the iron(II/III) starting material.This is the first molecular system that both breaks and forms the triple bond of N2 at room temperature.These results highlight the ability of multi-iron species to decrease the energy barriers associated with the activation of strong bonds.

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Affiliation: Department of Chemistry, Yale University , 225 Prospect Street, New Haven, Connecticut 06520, United States.

ABSTRACT
The six-electron oxidation of two nitrides to N2 is a key step of ammonia synthesis and decomposition reactions on surfaces. In molecular complexes, nitride coupling has been observed with terminal nitrides, but not with bridging nitride complexes that more closely resemble catalytically important surface species. Further, nitride coupling has not been reported in systems where the nitrides are derived from N2. Here, we show that a molecular diiron(II) diiron(III) bis(nitride) complex reacts with Lewis bases, leading to the rapid six-electron oxidation of two bridging nitrides to form N2. Surprisingly, these mild reagents generate high yields of iron(I) products from the iron(II/III) starting material. This is the first molecular system that both breaks and forms the triple bond of N2 at room temperature. These results highlight the ability of multi-iron species to decrease the energy barriers associated with the activation of strong bonds.

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Key N2-Cleaving and N2-Forming Reactions inthe Multi-iron System
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sch2: Key N2-Cleaving and N2-Forming Reactions inthe Multi-iron System


A multi-iron system capable of rapid N2 formation and N2 cleavage.

MacLeod KC, Vinyard DJ, Holland PL - J. Am. Chem. Soc. (2014)

Key N2-Cleaving and N2-Forming Reactions inthe Multi-iron System
© Copyright Policy
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4353015&req=5

sch2: Key N2-Cleaving and N2-Forming Reactions inthe Multi-iron System
Bottom Line: Surprisingly, these mild reagents generate high yields of iron(I) products from the iron(II/III) starting material.This is the first molecular system that both breaks and forms the triple bond of N2 at room temperature.These results highlight the ability of multi-iron species to decrease the energy barriers associated with the activation of strong bonds.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, Yale University , 225 Prospect Street, New Haven, Connecticut 06520, United States.

ABSTRACT
The six-electron oxidation of two nitrides to N2 is a key step of ammonia synthesis and decomposition reactions on surfaces. In molecular complexes, nitride coupling has been observed with terminal nitrides, but not with bridging nitride complexes that more closely resemble catalytically important surface species. Further, nitride coupling has not been reported in systems where the nitrides are derived from N2. Here, we show that a molecular diiron(II) diiron(III) bis(nitride) complex reacts with Lewis bases, leading to the rapid six-electron oxidation of two bridging nitrides to form N2. Surprisingly, these mild reagents generate high yields of iron(I) products from the iron(II/III) starting material. This is the first molecular system that both breaks and forms the triple bond of N2 at room temperature. These results highlight the ability of multi-iron species to decrease the energy barriers associated with the activation of strong bonds.

Show MeSH