LONG-RANGE SPIN-DENSITY PROPAGATION IN SATURATED-HYDROCARBONS - 3-[N]STAFFYL RADICALS

AJ MCKINLEY, PN IBRAHIM, BALAJI, J MICHL

Research output: Contribution to journalArticle

26 Citations (Scopus)

Abstract

The bridgehead radicals derived from the first three [n]staffanes (n = 1-3), oligomers of [1.1.1]propellane, have been generated from the corresponding bromides, and their solution EPR spectra have been recorded. Remarkably long-range hyperfine coupling has been found to epsilon, zeta, and even iota hydrogens, in qualitative agreement with ab initio UHF calculations. The coupling to the bridgehead hydrogen is attenuated by a factor of about 25 per added bicyclo[1.1.1]pentane cage. The long-range propagation of spin density can be attributed to strong interaction between the orbitals used to make the exocyclic bonds in the 1 and 3 positions of each bicyclo[1.1.1]pentane cage. The situation can be understood simply in terms of a linear sigma-hyperconjugated chain of orbitals interacting through resonance integrals whose effective magnitude alternates in an about 1:5 ratio. A more detailed analysis is provided by considering the effect on the spin density of the various types of off-diagonal elements in the UHF Hartree-Fock matrix expressed in terms of maximally spin-paired natural bond orbitals (MSP-NBO). This permits a clean separation of through-space and through-bond interactions as well as further separation of each of these into contributions due to bond delocalization and those due to bond spin polarization.

Original languageEnglish
Pages (from-to)10631-10637
Number of pages7
JournalJournal of the American Chemical Society
Volume114
Issue number26
DOIs
Publication statusPublished - 16 Dec 1992
Externally publishedYes

Cite this

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title = "LONG-RANGE SPIN-DENSITY PROPAGATION IN SATURATED-HYDROCARBONS - 3-[N]STAFFYL RADICALS",
abstract = "The bridgehead radicals derived from the first three [n]staffanes (n = 1-3), oligomers of [1.1.1]propellane, have been generated from the corresponding bromides, and their solution EPR spectra have been recorded. Remarkably long-range hyperfine coupling has been found to epsilon, zeta, and even iota hydrogens, in qualitative agreement with ab initio UHF calculations. The coupling to the bridgehead hydrogen is attenuated by a factor of about 25 per added bicyclo[1.1.1]pentane cage. The long-range propagation of spin density can be attributed to strong interaction between the orbitals used to make the exocyclic bonds in the 1 and 3 positions of each bicyclo[1.1.1]pentane cage. The situation can be understood simply in terms of a linear sigma-hyperconjugated chain of orbitals interacting through resonance integrals whose effective magnitude alternates in an about 1:5 ratio. A more detailed analysis is provided by considering the effect on the spin density of the various types of off-diagonal elements in the UHF Hartree-Fock matrix expressed in terms of maximally spin-paired natural bond orbitals (MSP-NBO). This permits a clean separation of through-space and through-bond interactions as well as further separation of each of these into contributions due to bond delocalization and those due to bond spin polarization.",
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author = "AJ MCKINLEY and PN IBRAHIM and BALAJI and J MICHL",
year = "1992",
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LONG-RANGE SPIN-DENSITY PROPAGATION IN SATURATED-HYDROCARBONS - 3-[N]STAFFYL RADICALS. / MCKINLEY, AJ; IBRAHIM, PN; BALAJI; MICHL, J.

In: Journal of the American Chemical Society, Vol. 114, No. 26, 16.12.1992, p. 10631-10637.

Research output: Contribution to journalArticle

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T1 - LONG-RANGE SPIN-DENSITY PROPAGATION IN SATURATED-HYDROCARBONS - 3-[N]STAFFYL RADICALS

AU - MCKINLEY, AJ

AU - IBRAHIM, PN

AU - BALAJI, null

AU - MICHL, J

PY - 1992/12/16

Y1 - 1992/12/16

N2 - The bridgehead radicals derived from the first three [n]staffanes (n = 1-3), oligomers of [1.1.1]propellane, have been generated from the corresponding bromides, and their solution EPR spectra have been recorded. Remarkably long-range hyperfine coupling has been found to epsilon, zeta, and even iota hydrogens, in qualitative agreement with ab initio UHF calculations. The coupling to the bridgehead hydrogen is attenuated by a factor of about 25 per added bicyclo[1.1.1]pentane cage. The long-range propagation of spin density can be attributed to strong interaction between the orbitals used to make the exocyclic bonds in the 1 and 3 positions of each bicyclo[1.1.1]pentane cage. The situation can be understood simply in terms of a linear sigma-hyperconjugated chain of orbitals interacting through resonance integrals whose effective magnitude alternates in an about 1:5 ratio. A more detailed analysis is provided by considering the effect on the spin density of the various types of off-diagonal elements in the UHF Hartree-Fock matrix expressed in terms of maximally spin-paired natural bond orbitals (MSP-NBO). This permits a clean separation of through-space and through-bond interactions as well as further separation of each of these into contributions due to bond delocalization and those due to bond spin polarization.

AB - The bridgehead radicals derived from the first three [n]staffanes (n = 1-3), oligomers of [1.1.1]propellane, have been generated from the corresponding bromides, and their solution EPR spectra have been recorded. Remarkably long-range hyperfine coupling has been found to epsilon, zeta, and even iota hydrogens, in qualitative agreement with ab initio UHF calculations. The coupling to the bridgehead hydrogen is attenuated by a factor of about 25 per added bicyclo[1.1.1]pentane cage. The long-range propagation of spin density can be attributed to strong interaction between the orbitals used to make the exocyclic bonds in the 1 and 3 positions of each bicyclo[1.1.1]pentane cage. The situation can be understood simply in terms of a linear sigma-hyperconjugated chain of orbitals interacting through resonance integrals whose effective magnitude alternates in an about 1:5 ratio. A more detailed analysis is provided by considering the effect on the spin density of the various types of off-diagonal elements in the UHF Hartree-Fock matrix expressed in terms of maximally spin-paired natural bond orbitals (MSP-NBO). This permits a clean separation of through-space and through-bond interactions as well as further separation of each of these into contributions due to bond delocalization and those due to bond spin polarization.

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KW - SOLVOLYSIS

KW - ACIDS

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JF - Journal of the Amercian Chemical Society

SN - 0002-7863

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