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Zeitschrift für Naturforschung B

A Journal of Chemical Sciences

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Volume 70, Issue 2

Issues

Photochemisch induzierte C–C-Verknüpfungen zwischen einem Mangan-koordinierten Pentadienylliganden und Acetylen

Ernst-Christian Koch
  • Centre for Defence Chemistry, Cranfield University, Wellington Hall 198, Shrivenham, SN6 8LA, UK
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Guido J. Reiss
  • Corresponding author
  • Institut für Anorganische Chemie und Strukturchemie, Lehrstuhl für Material- und Strukturforschung, Heinrich-Heine-Universität Düsseldorf, Universitätsstraße 1, 40225 Düsseldorf, Germany
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Published Online: 2015-02-06 | DOI: https://doi.org/10.1515/znb-2014-0227

Abstract

Irradiation of tricarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)manganese (1) in tetrahydrofuran (THF) at 208 K affords the carmine solvent complex dicarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)(THF)manganese (2). Complex 2 thermally reacts with acetylene (3) to give tricarbonyl(η3:2-1,3-dimethyl-bicyclo[3.3.1]-3,6-nonadien-2-yl)manganese (4) and dicarbonyl(5-7,10-13-η-6,8-dimethyl-1,3,5,8,10,12-tridecahexaen-5-yl)manganese (5). The crystal structure of complex 4 was determined at room temperature [triclinic space group P1¯,a=7.6891(9), b=8.3860(8), c=10.5252(13) Å, α=93.000(9)°, β=93.390(10)°, γ= 108.032(8)°, V=642.43(13) Å3]. The manganese atom is trigonal-bipyramidally coordinated by three carbonyl ligands, one ethenylic and one allylic fragment. Consequently, the bicyclic olefin ligand 1,3-dimethyl-bicyclo[3.3.1]-3,6-nonadiene coordinates the manganese atom in a η3:2 mode. The constitution of complex 5 was deduced from IR data, elemental analysis, and 1H NMR spectra. For the formation of complexes 4 and 5, a reaction mechanism is proposed.

Keywords: acetylene; crystal structure; NMR spectroscopy; tricarbonylmanganese; photochemistry

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About the article

Corresponding author: Guido J. Reiss, Institut für Anorganische Chemie und Strukturchemie, Lehrstuhl für Material- und Strukturforschung, Heinrich-Heine-Universität Düsseldorf, Universitätsstraße 1, 40225 Düsseldorf, Germany, Fax: +49-211-81-14146, E-mail:


Received: 2014-09-20

Accepted: 2014-10-29

Published Online: 2015-02-06

Published in Print: 2015-02-01


Citation Information: Zeitschrift für Naturforschung B, Volume 70, Issue 2, Pages 143–150, ISSN (Online) 1865-7117, ISSN (Print) 0932-0776, DOI: https://doi.org/10.1515/znb-2014-0227.

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