Possible nitrogen fixation by disilabutadiene

Kazunari Yoshizawa, Yoshihito Shiota, Songyun Kang, Tokio Yamabe

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

A possible nitrogen fixation based on a Diels-Alder reaction of 1,4-disila-1,3-butadiene and N2 is discussed. The activation energy from the reactants to the product, a six-membered ring of C2Si2N2, was computed to be only 5.1 kcal/mol at the B3LYP/6-311G** level of density functional theory. QCISD(T)/6-31G**//CASSCF/6-31G** calculations also gave 8.0 kcal/mol comparable to the B3LYP value. These computed activation energies are smaller than that of the well-known Diels-Alder reaction of butadiene and ethylene, 24.8 kcal/mol at the B3LYP/6-31G* level (Goldstein, E.; Beno, B.; Houk, K. N. J. Am. Chem. Soc. 1996, 118, 6036), and consequently, this unique reaction would proceed under mild conditions if this reactive species, disilabutadiene, is prepared. The triple bond of N2 is partially cleaved in a reductive manner to lead to the formation of an N=N double bond. Orbital interaction analyses suggest that one of the degenerate π* LUMOs of N2 has a good interaction with the high-lying HOMO of disilabutadiene, and this interaction should contribute to significant electron transfer from disilabutadiene to N2. 1,4-Disila-1,3-butadiene, could be prepared by thermal ring opening of 1,2-disilacyclobutene; the activation barrier for a symmetry-allowed conrotatory process of the two silylene groups was calculated to be 40.9 kcal/mol at the B3LYP/6-311G** level and 47.6 kcal/mol at the QCISD(T)/6-31G**//CASSCF/6-31G** level. We, thus, expect the artificial nitrogen fixation to occur when 1,2-disilacyclobutene and N2 gas are heat-treated in a sealed tube.

Original languageEnglish
Pages (from-to)5058-5063
Number of pages6
JournalOrganometallics
Volume16
Issue number23
DOIs
Publication statusPublished - Nov 11 1997
Externally publishedYes

Fingerprint

Nitrogen fixation
nitrogenation
butadiene
Diels-Alder reactions
Activation energy
activation energy
Density functional theory
rings
interactions
Gases
Chemical activation
electron transfer
ethylene
Electrons
activation
density functional theory
tubes
orbitals
heat
1,3-butadiene

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Possible nitrogen fixation by disilabutadiene. / Yoshizawa, Kazunari; Shiota, Yoshihito; Kang, Songyun; Yamabe, Tokio.

In: Organometallics, Vol. 16, No. 23, 11.11.1997, p. 5058-5063.

Research output: Contribution to journalArticle

Yoshizawa, Kazunari ; Shiota, Yoshihito ; Kang, Songyun ; Yamabe, Tokio. / Possible nitrogen fixation by disilabutadiene. In: Organometallics. 1997 ; Vol. 16, No. 23. pp. 5058-5063.
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abstract = "A possible nitrogen fixation based on a Diels-Alder reaction of 1,4-disila-1,3-butadiene and N2 is discussed. The activation energy from the reactants to the product, a six-membered ring of C2Si2N2, was computed to be only 5.1 kcal/mol at the B3LYP/6-311G** level of density functional theory. QCISD(T)/6-31G**//CASSCF/6-31G** calculations also gave 8.0 kcal/mol comparable to the B3LYP value. These computed activation energies are smaller than that of the well-known Diels-Alder reaction of butadiene and ethylene, 24.8 kcal/mol at the B3LYP/6-31G* level (Goldstein, E.; Beno, B.; Houk, K. N. J. Am. Chem. Soc. 1996, 118, 6036), and consequently, this unique reaction would proceed under mild conditions if this reactive species, disilabutadiene, is prepared. The triple bond of N2 is partially cleaved in a reductive manner to lead to the formation of an N=N double bond. Orbital interaction analyses suggest that one of the degenerate π* LUMOs of N2 has a good interaction with the high-lying HOMO of disilabutadiene, and this interaction should contribute to significant electron transfer from disilabutadiene to N2. 1,4-Disila-1,3-butadiene, could be prepared by thermal ring opening of 1,2-disilacyclobutene; the activation barrier for a symmetry-allowed conrotatory process of the two silylene groups was calculated to be 40.9 kcal/mol at the B3LYP/6-311G** level and 47.6 kcal/mol at the QCISD(T)/6-31G**//CASSCF/6-31G** level. We, thus, expect the artificial nitrogen fixation to occur when 1,2-disilacyclobutene and N2 gas are heat-treated in a sealed tube.",
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N2 - A possible nitrogen fixation based on a Diels-Alder reaction of 1,4-disila-1,3-butadiene and N2 is discussed. The activation energy from the reactants to the product, a six-membered ring of C2Si2N2, was computed to be only 5.1 kcal/mol at the B3LYP/6-311G** level of density functional theory. QCISD(T)/6-31G**//CASSCF/6-31G** calculations also gave 8.0 kcal/mol comparable to the B3LYP value. These computed activation energies are smaller than that of the well-known Diels-Alder reaction of butadiene and ethylene, 24.8 kcal/mol at the B3LYP/6-31G* level (Goldstein, E.; Beno, B.; Houk, K. N. J. Am. Chem. Soc. 1996, 118, 6036), and consequently, this unique reaction would proceed under mild conditions if this reactive species, disilabutadiene, is prepared. The triple bond of N2 is partially cleaved in a reductive manner to lead to the formation of an N=N double bond. Orbital interaction analyses suggest that one of the degenerate π* LUMOs of N2 has a good interaction with the high-lying HOMO of disilabutadiene, and this interaction should contribute to significant electron transfer from disilabutadiene to N2. 1,4-Disila-1,3-butadiene, could be prepared by thermal ring opening of 1,2-disilacyclobutene; the activation barrier for a symmetry-allowed conrotatory process of the two silylene groups was calculated to be 40.9 kcal/mol at the B3LYP/6-311G** level and 47.6 kcal/mol at the QCISD(T)/6-31G**//CASSCF/6-31G** level. We, thus, expect the artificial nitrogen fixation to occur when 1,2-disilacyclobutene and N2 gas are heat-treated in a sealed tube.

AB - A possible nitrogen fixation based on a Diels-Alder reaction of 1,4-disila-1,3-butadiene and N2 is discussed. The activation energy from the reactants to the product, a six-membered ring of C2Si2N2, was computed to be only 5.1 kcal/mol at the B3LYP/6-311G** level of density functional theory. QCISD(T)/6-31G**//CASSCF/6-31G** calculations also gave 8.0 kcal/mol comparable to the B3LYP value. These computed activation energies are smaller than that of the well-known Diels-Alder reaction of butadiene and ethylene, 24.8 kcal/mol at the B3LYP/6-31G* level (Goldstein, E.; Beno, B.; Houk, K. N. J. Am. Chem. Soc. 1996, 118, 6036), and consequently, this unique reaction would proceed under mild conditions if this reactive species, disilabutadiene, is prepared. The triple bond of N2 is partially cleaved in a reductive manner to lead to the formation of an N=N double bond. Orbital interaction analyses suggest that one of the degenerate π* LUMOs of N2 has a good interaction with the high-lying HOMO of disilabutadiene, and this interaction should contribute to significant electron transfer from disilabutadiene to N2. 1,4-Disila-1,3-butadiene, could be prepared by thermal ring opening of 1,2-disilacyclobutene; the activation barrier for a symmetry-allowed conrotatory process of the two silylene groups was calculated to be 40.9 kcal/mol at the B3LYP/6-311G** level and 47.6 kcal/mol at the QCISD(T)/6-31G**//CASSCF/6-31G** level. We, thus, expect the artificial nitrogen fixation to occur when 1,2-disilacyclobutene and N2 gas are heat-treated in a sealed tube.

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