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Abstract:

A model for the mechanism of formation of ladder structures for lithium amides is provided by the title compound 1, the first oligomeric mixed complex of a lithium amide with an amine (structure depicted to the right, where one piperidine ligand has been omitted from each of Li1 and Li2). The structure in the solid state is in accord with results of calculations on similar 1:1 complexes as well as with 13C NMR studies in solution. Reactions of lithium piperidide with CO in the presence of piperidine also suggest that such complexes are reactive intermediates. (Figure Presented.) Copyright © 1992 by VCH Verlagsgesellschaft mbH, Germany

Registro:

Documento: Artículo
Título:[Lithium Piperidide–Piperidine]4: Crystal Structure of an Oligomeric 1:1 Lithium Amide–Amine Mixed Complex, an Intermediate in the N‐Lithiation of Amines
Autor:Boche, G.; Langlotz, I.; Marsch, M.; Harms, K.; Nudelman, N.E.S.
Filiación:Fachbereich Chemie, Universität Marburg, Hans‐Meerwein‐Strasse, D-W-3550, Germany
Facultad de Ciencias Exactas Y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Buenos Aires, 1428, Argentina
Año:1992
Volumen:31
Número:9
Página de inicio:1205
Página de fin:1207
DOI: http://dx.doi.org/10.1002/anie.199212051
Título revista:Angewandte Chemie International Edition in English
Título revista abreviado:Angew. Chem. Int. Ed. Engl.
ISSN:05700833
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_05700833_v31_n9_p1205_Boche

Referencias:

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  • Gregory, K., Schleyer, Snaith, R., (1991) Adv. Inorg. Chem., 37, pp. 47-142. , Review
  • Gilchrist, J.H., Collum, D.B., (1992) J. Am. Chem. Soc., 114, pp. 794-795
  • Hall, P.L., Gilchrist, J.H., Harrison, A.T., Fuller, D.J., Collum, D.B., (1991) J. Am. Chem. Soc., 113. , 9575–9585, and references cited therein
  • Wanat, R.A., Collum, D.B., Van Duyne, G., Clardy, J., De Pue, R.T., (1986) J. Am. Chem. Soc., 108, p. 3422. , 3415
  • Sato, D., Kawasaki, H., Shimada, I., Arata, Y., Okamura, K., Date, T., Koga, K., (1992) J. Am. Chem. Soc., 114, pp. 761-763
  • Jackman, L.M., Scarmoutzos, L.M., Smith, B.D., Williard, P.G., (1988) J. Am. Chem. Soc., 110, pp. 6058-6063
  • Nudelman, N.S., (1989) Carbonylation of Main‐Group Organometallic Compounds in The Chemistry of Double‐Bonded Functional Groups, pp. 799-962. , Review:, S. Patai, Wiley, Chichester
  • Nudelman, N.S., Lewkowicz, E.S., Pérez, D.G., (1990), Synthesis, 917–920; Pérez, D.G., Nudelman, N.S., (1983) J. Org. Chem., 48, pp. 133-134
  • Furlong, J.J.P., Lewkowicz, E.S., Nudelman, N.S., (1990), J. Chem. Soc. Perkin Trans 2, 1461–1465; Nudelman, N.S., Pérez, D.G., (1989), J. Chem. Soc. Perkin Trans 2, 931–936; Rautenstrauch, V., Joyeux, M., (1979) Angew. Chem., 91. , 73–74
  • (1979) Angew. Chem. Int. Ed. Engl., 18. , 85
  • Pérez, D.G., Nudelman, N.S., (1988) J. Org. Chem., 53, pp. 408-413
  • Nudelman, N.S., Lewkowicz, E., Furlong, J.J.P., J. Org. Chem; Barr, D., Clegg, W., Mulvey, R.E., Snaith, R., (1984), J. Chem. Soc. Chem. Commun., 469–470; Clegg, W., MacGregor, M., Mulvey, R.E., O'Neil, P.A., (1992) Angew. Chem., 104, pp. 74-76
  • (1992) Angew. Chem. Int. Ed. Engl., 31. , 93
  • Crystal data for [1‐Li · 1‐H]4:(C40H84Li4N8), orthorhombic space group Pna21, a = 22.077(1), b = 12.230(1), c = 16.528(1) Å. Data collection with an Enraf‐Nonius CAD4 diffractometer, CuKα radiation, 193 K, 6086 measured reflections, 5578 independent, 4295 observed (F0 > 4σF0). Solution and refinement with the Siemens SHELXTL‐PLUS package (direct methods) [12–14]. One solvent molecule is twofold disordered (0.54:0.46). Disordered positions have been refined with isotropic temperature factors, the other non‐hydrogen atoms anisotropic, hydrogen atoms with common isotropic temperature factors, C‐bonded and disordered N‐bonded H atoms riding, other N‐bonded H atoms have been refined. 477 parameters, R = 0.0606, wR = 0.0491. An absolute structure could not be determined. Further details of the crystal structure investigation may be obtained from the Fachinformationszentrum Karlsruhe, Gesellschaft für wissenschaft‐lich‐technische Information mbH, D‐W‐7514 Eggenstein‐Leopoldshafen 2 (FRG) on quoting the deposition number CSD 320 464, the names of the authors, and the journal citation; SHELXTL‐PLUS (VMS), Release 4.2, Siemens Analytical Instruments, 1991; Spek, A.L., PLATON 88, Program for Geometrical Analysis of Crystal Structures, Utrecht, 1988; Keller, E., SCHAKAL‐88B, A FORTRAN Program for the Graphic Representation of Molecular and Crystallographic Models, Freiburg, 1988; Armstrong, D.R., Barr, D., Clegg, W., Hodgson, S.M., Mulvey, R.E., Reed, D., Snaith, R., Wright, D.S., (1989) J. Am. Chem. Soc., 111, pp. 4719-4727
  • Armstrong, D.R., Mulvey, R.E., Walker, G.T., Barr, D., Snaith, R., Clegg, W., Reed, D., (1988), J. Chem. Soc. Dalton Trans., 617–628; Armstrong, D.R., Barr, D., Clegg, W., Mulvey, R.E., Reed, D., Snaith, R., Wade, K., (1986), J. Chem. Soc. Chem. Commun., 869–870; It is probably long lithium amide ladders that precipitate from the solution immediately after the last complexing amine molecules have been lithiated [1, 2]

Citas:

---------- APA ----------
Boche, G., Langlotz, I., Marsch, M., Harms, K. & Nudelman, N.E.S. (1992) . [Lithium Piperidide–Piperidine]4: Crystal Structure of an Oligomeric 1:1 Lithium Amide–Amine Mixed Complex, an Intermediate in the N‐Lithiation of Amines. Angewandte Chemie International Edition in English, 31(9), 1205-1207.
http://dx.doi.org/10.1002/anie.199212051
---------- CHICAGO ----------
Boche, G., Langlotz, I., Marsch, M., Harms, K., Nudelman, N.E.S. "[Lithium Piperidide–Piperidine]4: Crystal Structure of an Oligomeric 1:1 Lithium Amide–Amine Mixed Complex, an Intermediate in the N‐Lithiation of Amines" . Angewandte Chemie International Edition in English 31, no. 9 (1992) : 1205-1207.
http://dx.doi.org/10.1002/anie.199212051
---------- MLA ----------
Boche, G., Langlotz, I., Marsch, M., Harms, K., Nudelman, N.E.S. "[Lithium Piperidide–Piperidine]4: Crystal Structure of an Oligomeric 1:1 Lithium Amide–Amine Mixed Complex, an Intermediate in the N‐Lithiation of Amines" . Angewandte Chemie International Edition in English, vol. 31, no. 9, 1992, pp. 1205-1207.
http://dx.doi.org/10.1002/anie.199212051
---------- VANCOUVER ----------
Boche, G., Langlotz, I., Marsch, M., Harms, K., Nudelman, N.E.S. [Lithium Piperidide–Piperidine]4: Crystal Structure of an Oligomeric 1:1 Lithium Amide–Amine Mixed Complex, an Intermediate in the N‐Lithiation of Amines. Angew. Chem. Int. Ed. Engl. 1992;31(9):1205-1207.
http://dx.doi.org/10.1002/anie.199212051