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Correlated rotation of aryl substituents in diarylmethyl-, diarylphosphine- and related fragments. An empirical force field study

Korrelierte Rotation von Arylringen in Diarylmethyl-, Diarylphosphin- und verwandten Fragmenten. Eine Untersuchung mit Hilfe der empirischen Kraftfeldmethode

  • Organische Chemie Und Biochemie
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Summary

Ground state structures and conformational interconversion mechanisms of 25 diaryl compoundsAr 2 Z (Z=CH2, CHR, CH(OH), P-CH3) were analyzed. For tetra(ortho-alkyl)substituted diaryls the cogwheeling mechanism was found as the threshold mechanism. A shift from the cogwheeling mechanism to interconversions via 2-ring flips is found in di(ortho-alkyl)substituted compounds. The ground state structures and interconversion mechanisms of diarylmethylphosphines are very similar to those of the related 1,1-diarylethanes. The interconversion barrier for correlated conrotation of the aryl rings in di(tert-butylphenyl)methanol (20) was measured by low temperature NMR and is in excellent agreement with the calculated value for the 2-ring flipT″2 (ΔG≠ (exp.)=48 kJ mol−1; ΔG≠ (calc.)=54 kJ mol−1).

Zusammenfassung

Die Grundzustandskonformationen und die konformativen Interkonversions-mechanismen von 25 DiarylverbindungenAr 2 Z (Z=CH2, CHR, CH(OH), P-CH3) wurden analysiert. Für tetra(ortho-alkyl)substituierte Diaryle wurde der cogwheeling-Mechanismus als der Interkonversionsmechanismus niedrigster Energie ermittelt. In di(ortho-alkyl)substituierten Verbindungen werden nicht der cogwheeling-Mechanismus sondern 2-ring flips als Interkonversionsmechanismen gefunden. Die Grundzustände und Interkonversionsmechanismen für Diarylmethylphosphine sind sehr ähnlich jenen der verwandten 1,1-Diarylethane. Die Interkonversionsbarriere für die korrelierte Bewegung der Arylringe von Di(tert-butylphenyl)methanol (20) wurde mittels Tieftemperatur-NMR-Spektroskopie ermittelt und ist in sehr guter Übereinstimmung mit dem berechneten Wert für den 2-Ring flipT″2 (ΔG≠ (exp.)=48 kJ mol−1; ΔG≠ (calc.)=54 kJ mol−1).

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  1. Institut für Organische Chemie, Universität Wien, A-1090, Wien, Austria

    W. Weissensteiner

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Weissensteiner, W. Correlated rotation of aryl substituents in diarylmethyl-, diarylphosphine- and related fragments. An empirical force field study. Monatsh Chem 123, 1135–1147 (1992). https://doi.org/10.1007/BF00808276

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  • DOI: https://doi.org/10.1007/BF00808276

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