Synthesis and Nonlinear Optical Properties of New Heptapentaenylidene Complexes :  Study on the Second Harmonic Generation Efficiencies of Amino-Substituted Group 6 Cumulenylidenes

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1998
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Roth, Gerhard
Meyer-Friedrichsen, Timo
Heck, Jürgen
Houbrechts, Stephan
Persoons, Andé
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Reaction of the ynamine MeCCNEt2 with the pentatetraenylidene complexes [(CO)5MCCCCC(NMe2)2] (M = Cr (3a), W (3b)) at room temperature affords the new heptapentaenylidene complexes [(CO)5MCCCCC(NEt2)C(Me)C(NMe2)2] (M = Cr (5a), W (5b)) in good yield. The spectroscopic data and the X-ray structural analysis of 5a indicate that these amino-substituted metallacumulenes are best described as hybrids of a cumulene and several strongly polarized alkynyl structures. For 5a and the related metallacumulenes [(CO)5MCCC(NMe2)2] (M = Cr (1a), W (1b)), [(CO)5CrCCC(NEt2)C(H)C(NMe2)2] (2a), and 3a,b the molecular first hyperpolarizability β was determined by hyper-Rayleigh scattering experiments. The insertion of a cumulated C2 unit into a metallacumulene quadruples β, while the insertion of a conjugated C2 unit results in only slight enhancement of the second harmonic generation response. Substitution of tungsten for chromium has only a minor effect on β. All observed β values are reasonably high compared with those of other organometallic compounds.

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ISO 690ROTH, Gerhard, Helmut FISCHER, Timo MEYER-FRIEDRICHSEN, Jürgen HECK, Stephan HOUBRECHTS, Andé PERSOONS, 1998. Synthesis and Nonlinear Optical Properties of New Heptapentaenylidene Complexes :  Study on the Second Harmonic Generation Efficiencies of Amino-Substituted Group 6 Cumulenylidenes. In: Organometallics. 1998, 17(8), pp. 1511-1516. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om970896p
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@article{Roth1998Synth-23049,
  year={1998},
  doi={10.1021/om970896p},
  title={Synthesis and Nonlinear Optical Properties of New Heptapentaenylidene Complexes :  Study on the Second Harmonic Generation Efficiencies of Amino-Substituted Group 6 Cumulenylidenes},
  number={8},
  volume={17},
  issn={0276-7333},
  journal={Organometallics},
  pages={1511--1516},
  author={Roth, Gerhard and Fischer, Helmut and Meyer-Friedrichsen, Timo and Heck, Jürgen and Houbrechts, Stephan and Persoons, Andé}
}
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