Crystal structure of [2-ZnCl-benzoxazole·2THF]2: The remarkable difference between 2-ZnHal- and 2-Li-oxazoles

Chemistry - A European Journal

Volumn 4, Issue 5, 1998, Pages 814-817

  Boche, Gernot ^a   Bosold, Ferdinand ^a   Hermann, Holger ^a   Marsch, Michael ^a   Harms, Klaus ^a   Lohrenz, J C W ^a  

^a PHILIPPS UNIVERSITY MARBURG   (Germany)

Author keywords

Benzoxazole; Carbene complexes; Lithium; Quantum chemical calculations; Zinc

Indexed keywords

EID: 0031802303     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3765(19980515)4:5<814::AID-CHEM814>3.0.CO;2-F     Document Type: Article

References (42)

1. 2 is also reported in this work.
2. 2 is also reported in this work.
3. 2 is also reported in this work.
4. 2 is also reported in this work.
5. 2 is also reported in this work.
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7. a) F. Bosold, P. Zulauf, M. Marsch, K. Harms, J. Lohrenz, G. Boche, Angew. Chem. 1991, 103, 1497-1499; Angew. Chem. Int. Ed. Engl. 1991, 30, 1455-1457;
8. b) G. Boche, F. Haller, K. Harms, D. Hoppe, W. Koch, J. Lohrenz, M. Marsch, A. Opel, C. Thümmler, O. Zschage in New Aspects of Organic Chemistry II. Organic Synthesis for Materials and Life Sciences. Proceedings of the Fifth International Kyoto Conference on New Aspects of Organic Chemistry, Nov. 11-15, 1991 (Eds.: Z. Yoshida, Y. Ohshiro), VCH, Weinheim/Kodansha Ltd., Tokyo, 1992, pp. 159-179.
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11. +-carbene complex is formed (A. J. Arduengo III, M. Tamm, personal communication, as discussed in ref. [12]).
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14. 3-benzoxazole lithiate complex;
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20. Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-100713. Copies of the data can be obtained free of charge on application to The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: (+44)1223 336-033; e-mail: deposit@ccdc.cam.ac.uk).
21. Cambridge Structural Data Base, update April 1997. The structure of benzoxazole is not reported in the literature.
22. -1, respectively) than their acyclic isomers.
23. 2O at C2.
24. The ab initio calculations were performed with the Gaussian 94 program package. All structures (ref. [15]) were optimized with the hybrid density functional B3LYP and identified as energy minima by the fact that the eigenvalues in the Hessian matrices were only positive. Calculations on the MP2 level did not give structurally or energetically significant differences. A standard 6-31 + G(d) basis set was used for the atoms H, C, N, O, and Li. The Zn and Cl atoms were calculated with the following ECPs and valence basis sets : Zn, 311111/ 22111/411/1; Cl, 31/211. See: A. Bergner, M. Dolg, W. Kuechle, H. Stoll, H. Preuss, Mol. Phys. 1993, 80, 1431; M. Dolg, U. Wedig, H. Stoll, H. Preuss, J. Chem. Phys. 1987, 86, 866.
25. The ab initio calculations were performed with the Gaussian 94 program package. All structures (ref. [15]) were optimized with the hybrid density functional B3LYP and identified as energy minima by the fact that the eigenvalues in the Hessian matrices were only positive. Calculations on the MP2 level did not give structurally or energetically significant differences. A standard 6-31 + G(d) basis set was used for the atoms H, C, N, O, and Li. The Zn and Cl atoms were calculated with the following ECPs and valence basis sets : Zn, 311111/ 22111/411/1; Cl, 31/211. See: A. Bergner, M. Dolg, W. Kuechle, H. Stoll, H. Preuss, Mol. Phys. 1993, 80, 1431; M. Dolg, U. Wedig, H. Stoll, H. Preuss, J. Chem. Phys. 1987, 86, 866.
26. -1) and the rotation was barrierless, no further geometry optimization was attempted in this case.
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28. 2Mg; they detected higher charge separation in the Mg case. For further theoretical investigations on C-Zn bonds, see: I. Antes, G. Frenking, Organometallics 1995, 14, 4263-4268, and references therein.
29. 2Mg; they detected higher charge separation in the Mg case. For further theoretical investigations on C-Zn bonds, see: I. Antes, G. Frenking, Organometallics 1995, 14, 4263-4268, and references therein.
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31. b) Review article: A. Streitwieser Jr., S. M. Bachrach, A. Dorigo, P. von R. Schleyer, in Lithium Chemistry, A Theoretical and Experimental Overview (Eds.: A.-M. Sapse, P. von R. Schleyer), Wiley, New York, 1995.
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42. - on the structure and reactivity of Li and ZnHal carbenoids will be reported elsewhere.