Type of Publication: | Journal article |
Author: | Fischer, Helmut; Rädler, Michael; Mosbacher, Alexander; Drexler, Matthias; Hübner, Eike; Weibert, Bernhard; Heck, Jürgen; Wittenberg, Christian; Steffens, Stefan |
Year of publication: | 2007 |
Published in: | Collection of Czechoslovak Chemical Communications ; 72 (2007), 4. - pp. 503-526. - ISSN 0010-0765. - eISSN 1212-6950 |
DOI (citable link): | https://dx.doi.org/10.1135/cccc20070503 |
Summary: |
The reaction of [(CO)5M(thf)] with but-3-yn-1-ols in the presence of NEt3 offers a convenient route to 2-oxacyclopentylidene complexes [(CO)5M=C-O-CH2CH2CH2] (M = Cr (1a), W (1b)) in yields up to 96%. Furthermore, the reaction of 1 with ω-(dimethylamino)- substituted enals, Me2N-(CH=CH)n-C(=O)H, activated by Me3SiCl/NEt3 or POCl3/NEt3 gives via aldol condensation the unsaturated oxacyclic push-pull carbene complexes [(CO)5M=C-O-CH2CH2C{=CH-(CH=CH)n-NMe2}] (n = 0 (2), 1 (3), 2 (4), 3 (5)). In 2-5, the amino group acts as an electron-donor unit and the oxacyclic carbene pentacarbonyl moiety as an electron acceptor. The aminometallaenes 2-5 have been characterized spectroscopically, the chromium complexes 2a-5a additionally by X-ray structure analysis. For some complexes, their nonlinear optical properties (second harmonic generation) have been studied and β values up to 58 × 10-30 esu have been determined. The results of DFT calculations on chromium complexes 2a-5a show that on lengthening of the unsaturated chain the influence of the carbonyl-metal fragment on the polyunsaturated chain strongly decreases.
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Subject (DDC): | 540 Chemistry |
Bibliography of Konstanz: | Yes |
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FISCHER, Helmut, Michael RÄDLER, Alexander MOSBACHER, Matthias DREXLER, Eike HÜBNER, Bernhard WEIBERT, Jürgen HECK, Christian WITTENBERG, Stefan STEFFENS, 2007. Conjugated Polyunsaturated Oxacyclic Carbene Complexes : Synthesis, Structure, and Properties. In: Collection of Czechoslovak Chemical Communications. 72(4), pp. 503-526. ISSN 0010-0765. eISSN 1212-6950. Available under: doi: 10.1135/cccc20070503
@article{Fischer2007Conju-22830, title={Conjugated Polyunsaturated Oxacyclic Carbene Complexes : Synthesis, Structure, and Properties}, year={2007}, doi={10.1135/cccc20070503}, number={4}, volume={72}, issn={0010-0765}, journal={Collection of Czechoslovak Chemical Communications}, pages={503--526}, author={Fischer, Helmut and Rädler, Michael and Mosbacher, Alexander and Drexler, Matthias and Hübner, Eike and Weibert, Bernhard and Heck, Jürgen and Wittenberg, Christian and Steffens, Stefan} }
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