Substituent‐Controlled Reactions of Iminophosphoranes with Methyllithium
1995; Wiley; Volume: 34; Issue: 16 Linguagem: Inglês
10.1002/anie.199517521
ISSN1521-3773
AutoresAlexander Steiner, Dietmar Stalke,
Tópico(s)Ferrocene Chemistry and Applications
ResumoAngewandte Chemie International Edition in EnglishVolume 34, Issue 16 p. 1752-1755 Communication Substituent-Controlled Reactions of Iminophosphoranes with Methyllithium†‡ Dr. Alexander Steiner, Dr. Alexander Steiner Institut für Anorganische Chemie der Universität, Tammannstrasse 4, D-37077 Göttingen (Germany). Telefax: Int. code + (551)392582Search for more papers by this authorPriv.-Doz. Dr. Dietmar Stalke, Corresponding Author Priv.-Doz. Dr. Dietmar Stalke Institut für Anorganische Chemie der Universität, Tammannstrasse 4, D-37077 Göttingen (Germany). Telefax: Int. code + (551)392582Institut für Anorganische Chemie der Universität Tammannstrasse 4, D-37077 Göttingen (Germany). Telefax: Int. code + (551)392582Search for more papers by this author Dr. Alexander Steiner, Dr. Alexander Steiner Institut für Anorganische Chemie der Universität, Tammannstrasse 4, D-37077 Göttingen (Germany). Telefax: Int. code + (551)392582Search for more papers by this authorPriv.-Doz. Dr. Dietmar Stalke, Corresponding Author Priv.-Doz. Dr. Dietmar Stalke Institut für Anorganische Chemie der Universität, Tammannstrasse 4, D-37077 Göttingen (Germany). Telefax: Int. code + (551)392582Institut für Anorganische Chemie der Universität Tammannstrasse 4, D-37077 Göttingen (Germany). Telefax: Int. code + (551)392582Search for more papers by this author First published: September 1, 1995 https://doi.org/10.1002/anie.199517521Citations: 71 † This work was supported by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie. ‡ Dedicated to Professor Paul von Ragué Schleyer on the occasion of his 65th birthday AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract Totally different reactivity is observed in the reactions of the two isoelectronic iminophosphoranes Py3P NSiMe3 (Py = 2-pyridyl) and Ph3P NSiMe3 with methyllithium. While the first, even at −78 °C, spontaneously yields a monomeric amide on reduction of phosphorus(V) to phosphorus(III), the triphenyliminophosphorane yields the dimer 1 only after several days at room temperature in a deprotonation reaction of one phenyl ring in the ortho position. References 1 S. Oae, Y. Uchida, Acc. Chem. Res. 1991, 24, 202. 2 K. B. Dillon, Chem. Rev. 1994, 94, 1441. 3 G. Wittig, Pure Appl. Chem. 1964, 9, 245. 4 Y. Uchida, K. Onoue, N. Tada, F. Nagao, S. Oae, Tetrahedron Lett. 1989, 30, 567. 5(a) G. Wittig, A. Maercker, J. Organomet. Chem. 1967, 8, 491; (b) E. P. Kyba, J. Am. Chem. Soc. 1976, 98, 4805. 6(a) Y. Uchida, M. Kawai, H. Masauji, S. Oae, Heteroatom Chem. 1993, 4, 421; (b) Y. Uchida, Y. Takaya, S. Oae, Heterocycles 1990, 30, 347. 7(a) A. Steiner, D. Stalke, J. Chem. Soc. Chem. Commun. 1993, 444; (b) A. Steiner, D. Stalke, Organometallics, 1995, 14, 2422. 8 A. W. Johnson, Ylides and Imines of Phosphorus, Wiley, New York, 1993. 9 Crystallographic data for 3: C19H24LiN4PSi, M = 374.4, triclinic, space group P1, a = 906.3(4), b = 958.1(4), c = 1378.7(6) pm, α = 73.43(2), β = 72.48(2), γ = 74.81(2)°, V = 1.0737 nm3, Z = 2, ρcalcd = 1.158 Mg m−3, λ = 71.073 pm, T = 153(2)K, μ(MoKα) = 0.193 mm−1. All data were collected by using an oil-coated shock-cooled crystal [23] with dimensions of 0.6 × 0.4 × 0.3 mm in the range 8°≥ 2θ ≥ 50° on a Stoe-Siemens AED diffractometer. Of the 4461 collected reflections, 3371 were unique. The structure was solved by direct methods [24] and refined by full-matrix least-squares on F2 [25]. R1 = (I > 2σ (I)) = 0.061 and wR2 = 0.180 (all data) with R1 = Σ|| Fo| | Fc||/Σ| Fo and wR2 = Σw(F– F)2/Σw((F)2)0.5; highest residual electron density peak: 948 e nm−3. Crystallographic data for 4: C46H56Li2N2OP2Si2, M = 784.9, monoclinic, space group P21/ c, a = 1482.81(1), b = 1691.9(2), c = 1806.0(2) pm, β = 4.42(1)°, V = 4.517 nm3, Z = 4, ρcalcd = 1.154 Mg m−3, λ = 71.073 pm, T = 173(2)K, μ(MoKα) = 0.184 mm−1. All data were collected by using an oil-coated shock-cooled crystal [23] with dimensions of 0.8 × 0.7 × 0.4 mm in the range of 8° ≥ 2θ ≥ 45° on a Stoe-Siemens AED diffractometer. Of the 6980 collected reflections, 5899 were unique. The structure was solved by direct methods [24] and refined by full-matrix least-squares on F2 [25]. R1 = (I > 2σ(I)) = 0.042 and wR2 = 0.110 (all data) with R1 = Σ|| Fo|–| Fc||/Σ| Fo| and wR2 = (Σw(F– F) 2/Σw(F)2)0.5; highest residual electron density peak: 349 e nm−3. Further details of the crystal structure investigations are available on request from the Director of the Cambridge Crystallographic Data Centre, 12 Union Road, GB-Cambridge CB2 1EZ (UK), on quoting the full journal citation. 10(a) G. Wittig, E. Kochendörfer, Angew. Chem. 1958, 70, 506; (b) G. Wittig, D. Hellwinkel Angew. Chem. 1962, 74, 76. 11 P. Rademacher Strukturen organischer Moleküle, VCH, Weinheim, 1987, p. 56. 12 E. Niecke, D. Gudat, Angew. Chem. 1991, 103, 251; Angew. Chem. Int. Ed. Engl. 1991, 30, 217. 13 M. T. Ashby, Z. Li, Inorg. Chem. 1992, 31, 1321. 14 G. Trinquier, M. T. Ashby, Inorg. Chem. 1994, 33, 1306. 15 U. Schümann, J. Kopf, E. Weiss, Angew. Chem. 1985, 97, 222; Angew. Chem. Int. Ed. Engl. 1985, 24, 215. 16(a) D. Thoennes, E. Weiss, Chem. Ber. 1978, 111, 3157; (b) H. Hope, P. P. Power, J. Am. Chem. Soc. 1983, 105, 5320. 17 A. Steiner, D. Stalke, Inorg. Chem. 1993, 32, 1977. 18 W. Setzer, P. von R. Schleyer, Adv. Organomet. Chem. 1985, 24, 353. 19 G. van Koten, Pure Appl. Chem. 1989, 61, 1681. 20 S. Wingerter, D. Stalke, unpublished results. 21 R. Fleischer, A. Steiner, D. Stalke, unpublished results. 22 H. Schmidbaur, W. Wolfsberger, Chem. Ber. 1967, 100, 1000. 23 T. Kottke, D. Stalke, J. Appl. Crystallogr. 1993, 26, 615. 24 G. M. Sheldrick, Acta Crystallogr. Sect. A 1990, 46, 467. 25 G. M. Sheldrick, SHELXL-93, program for crystal structure refinement, University of Göttingen, 1993. Citing Literature Volume34, Issue16September 1, 1995Pages 1752-1755 ReferencesRelatedInformation
Referência(s)