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Zeitschrift für Naturforschung B

A Journal of Chemical Sciences

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1865-7117
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Volume 51, Issue 10

Issues

Photochemische Reaktionen von Übergangsmetall-Organyl-Komplexen mit Olefinen, XVI [1]: Photochemisch induzierte Cycloadditionen von Diphenylacetylen an Tricarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)mangan / Photochemical Reactions of Transition Metal Organyl Complexes with Olefins, XVI [1]: Photochemically Induced Cycloadditions of Diphenylacetylene to Tricarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)manganese

Cornelius G. Kreiter
  • Fachbereich Chemie der Universität Kaiserslautern, Erwin Schrödinger-Straße, D-67663 Kaiserslautern
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Ernst-Christian Koch
  • Fachbereich Chemie der Universität Kaiserslautern, Erwin Schrödinger-Straße, D-67663 Kaiserslautern
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Walter Frank
  • Fachbereich Chemie der Universität Kaiserslautern, Erwin Schrödinger-Straße, D-67663 Kaiserslautern
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Guido J. Reiß
  • Fachbereich Chemie der Universität Kaiserslautern, Erwin Schrödinger-Straße, D-67663 Kaiserslautern
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
Published Online: 2014-06-02 | DOI: https://doi.org/10.1515/znb-1996-1019

Upon UV irradiation in THF at 208 K tricarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)- manganese (1) yields solvent stabilized, very reactive dicarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)(tetrahydrofuran)manganese (2), which reacts in situ with one or two molecules of diphenylacetylene (3) and yields four manganese complexes and 1,3-dimethyl-5,6-diphenyl-bicyclo[3.2.1]oct-2-ene-7-one (5), which were separated by HPL chromatography. In addition to tricarbonyl η5-4,6 -dimethyl-1,2-diphenyl-cyclohepta-2,4-dien-1-yl)manganese (4) formed by [5+2]cycloaddition and successive 1,4-H shift, tricarbonyl{ 1′,2′,5′-η-5-methyl-2,3 -diphenyl-5- (2′-methyl-4′,5′-diphenyl-penta-1′,4′-dien-1′,5′-diyl)cyclopent-2-en-1 -one-κ-O}manganese (6) is isolated with a ligand, formed from 2,4-dimethyl-2,4-pentadien-1-yl, two units of 3 and one carbon monoxide. The ligands of tricarbonyl{ 1-4,2′-η-4,6 -dimethyl-1,2-diphenyl-5-(E-1′,2′- diphenyl-vinylen)cyclohepta-1,3-diene}manganese (7), and tricarbonyl{η5-4,6 -dimethyl-1,2-diphenyl-7-(E-1′,2′-diphenyl-vinyl)cyclohepta-2,4-dien-1-yl}m anganese (8) are formed from 2,4-dimethyl-2,4-pentadien-1-yl and of two molecules of 3 each. The crystal and molecular structures of 5 and 6 have been determined by single crystal X-ray diffraction. 5 crystallizes in the triclinic space group P1̅ , a = 992.0(2) pm, b = 996.8(2) pm, c = 1021.0(2) pm, a = 77.67(3)°, β = 61.17(3)°, γ = 88.68(3)°. Complex 6 crystallizes also in the triclinic space group P1̅ ,a = 1023.2(2) pm, b - 1113.8(2) pm, c = 1567.9(3) pm, α = 82.88(3)°, β = 86.93(3)°, 7 = 63.53(3)°. The constitutions of 4, 7 and 8 were elucidated from the IR, NMR and mass spectra. Possible formation mechanisms for the compounds 4-8 are proposed. Complex 7 shows hindered rotations of two phenyl groups with different barriers of energy ΔG316 = 68.8 kJ/mol, „ΔH = 67.9 ± 0.7 kJ/mol, ΔS = -2 ± 2 J/mol · K and ΔG296 = 60.6 kJ/mol, ΔH = 57.7 ± 1.0 kJ/mol, ΔS = -10 ± 2 J/mol·K due to steric interactions.

: Tricarbonyl(η5-pentadienyl)manganese; Photoreaction. Diphenylacetylene; Cycloaddition

About the article

Received: 1996-04-18

Published Online: 2014-06-02

Published in Print: 1996-10-01


Citation Information: Zeitschrift für Naturforschung B, Volume 51, Issue 10, Pages 1473–1485, ISSN (Online) 1865-7117, ISSN (Print) 0932-0776, DOI: https://doi.org/10.1515/znb-1996-1019.

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© 1946 – 2014: Verlag der Zeitschrift für Naturforschung. This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License. BY-NC-ND 3.0

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