Synthesis and Structure of the First Dimeric Iminoalane Containing an Al 2 N 2 Heterocycle
1994; Wiley; Volume: 33; Issue: 9 Linguagem: Inglês
10.1002/anie.199409691
ISSN1521-3773
AutoresStephan Schulz, Ludger Häming, Regine Herbst‐Irmer, Herbert W. Roesky, George M. Sheldrick,
Tópico(s)Ferrocene Chemistry and Applications
ResumoAngewandte Chemie International Edition in EnglishVolume 33, Issue 9 p. 969-970 Communication Synthesis and Structure of the First Dimeric Iminoalane Containing an Al2N2 Heterocycle†‡ Dipl.-Chem. Stephan Schulz, Dipl.-Chem. Stephan Schulz Institut für Anorganische Chemie der Universität, Tammannstrasse 4, D-37077 Göttingen (FRG), Telefax: Int. code + (551)39-3373Search for more papers by this authorLudger Häming, Ludger Häming Institut für Anorganische Chemie der Universität, Tammannstrasse 4, D-37077 Göttingen (FRG), Telefax: Int. code + (551)39-3373Search for more papers by this authorDr. Regine Herbst-Irmer, Dr. Regine Herbst-Irmer Institut für Anorganische Chemie der Universität, Tammannstrasse 4, D-37077 Göttingen (FRG), Telefax: Int. code + (551)39-3373Search for more papers by this authorProf. Dr. Herbert W. Roesky, Corresponding Author Prof. Dr. Herbert W. Roesky Institut für Anorganische Chemie der Universität, Tammannstrasse 4, D-37077 Göttingen (FRG), Telefax: Int. code + (551)39-3373Institut für Anorganische Chemie der Universität, Tammannstrasse 4, D-37077 Göttingen (FRG), Telefax: Int. code + (551)39-3373Search for more papers by this authorProf. George M. Sheldrick, Prof. George M. Sheldrick Institut für Anorganische Chemie der Universität, Tammannstrasse 4, D-37077 Göttingen (FRG), Telefax: Int. code + (551)39-3373Search for more papers by this author Dipl.-Chem. Stephan Schulz, Dipl.-Chem. Stephan Schulz Institut für Anorganische Chemie der Universität, Tammannstrasse 4, D-37077 Göttingen (FRG), Telefax: Int. code + (551)39-3373Search for more papers by this authorLudger Häming, Ludger Häming Institut für Anorganische Chemie der Universität, Tammannstrasse 4, D-37077 Göttingen (FRG), Telefax: Int. code + (551)39-3373Search for more papers by this authorDr. Regine Herbst-Irmer, Dr. Regine Herbst-Irmer Institut für Anorganische Chemie der Universität, Tammannstrasse 4, D-37077 Göttingen (FRG), Telefax: Int. code + (551)39-3373Search for more papers by this authorProf. Dr. Herbert W. Roesky, Corresponding Author Prof. Dr. Herbert W. Roesky Institut für Anorganische Chemie der Universität, Tammannstrasse 4, D-37077 Göttingen (FRG), Telefax: Int. code + (551)39-3373Institut für Anorganische Chemie der Universität, Tammannstrasse 4, D-37077 Göttingen (FRG), Telefax: Int. code + (551)39-3373Search for more papers by this authorProf. George M. Sheldrick, Prof. George M. Sheldrick Institut für Anorganische Chemie der Universität, Tammannstrasse 4, D-37077 Göttingen (FRG), Telefax: Int. code + (551)39-3373Search for more papers by this author First published: May 18, 1994 https://doi.org/10.1002/anie.199409691Citations: 85 † This work was supported by the Deutsche Forschungsgemeinschaft, the Volkswagen-Stiftung, and the Fonds der Chemischen Industrie. ‡ Dedicated to Professor M. Frederick Hawthorne 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 An almost ideal planar Al2N2 ring as a central unit and the lowest degree of oligomerization for the class of compounds is shown by the dimeric iminoalane 1, which is formed from (Cp*Al)4 and Me3SiN3. The fact that no heterocubane results is attributed to the steric demand of the Cp* and SiMe3 groups. References 1 S. M. Sze, Physics of Semiconductor Devices, 2nd edition, Wiley, New York, 1981; C. R. M. Grovenor, Microelectronic Materials, Hilger, Philadelphia, PA, 1989; B. G. Streetman, Solid State Electronic Devices, 3rd edition, Prentice Hall, Englewood Cliffs, NJ, 1990; W. Rockensüss, H. W. Roesky, Adv. Mater. 1993, 5, 443. 2 T. Belgardt, H. W. Roesky, M. Noltemeyer, H.-G. Schmidt, Angew. Chem. 1993, 105, 1101; Angew. Chem. Int. Ed. Engl. 1993, 32, 1056. 3 G. Del Piero, M. Cesari, G. Dozzi, A. Mazzei, J. Organomet. Chem. 1977, 129, 281; T. R. R. McDonald, W. S. McDonald, Acta Crystallogr. Sect. B 1972, 28, 1619; K. M. Waggoner, P. P. Power, J. Am. Chem. Soc. 1991, 113, 3385; D. M. Choquette, M. J. Timm, J. L. Hobbs, T. M. Nicholson, M. M. Olmstead, R. P. Planalp, Inorg. Chem. 1993, 32, 2600. 4 M. Veith, Chem. Rev. 1990, 90, 3; M. Cesari, S. Cucinella in The Chemistry of Inorganic Homo- and Heterocycles, Vol. I (Eds.: I. Haiduc, D. B. Sowerby), Academic Press, London, 1987, p. 167. 5 K. M. Waggoner, H. Hope, P. P. Power, Angew. Chem. 1988, 100, 1765; Angew. Chem. Int. Ed. Engl. 1988, 27, 1699. 6 G. Del Piero, G. Perego, S. Cucinella, M. Cesari, A. Mazzei, J. Organomet. Chem. 1977, 136, 13; G. Del Piero, M. Cesari, G. Perego, S. Cucinella, E. Cernia, J. Organomet. Chem. 1977, 129, 289; S. Amirkhalili, P. B. Hitchkock, J. D. Smith, J. Chem. Soc. Dalton Trans. 1979, 1206. 7 P. B. Hitchkock, H. A. Jasim, M. F. Lappert, H. D. Williams, Polyhedron 1990, 245. 8 C. Dohmeier, C. Robl, M. Tacke, H. Schnöckel, Angew. Chem. 1991, 103, 594; Angew. Chem. Int. Ed. Engl. 1991, 30, 564. 9 S. Schulz, H. W. Roesky, H. J. Koch, G. M. Sheldrick, D. Stalke, A. Kuhn, Angew. Chem. 1993, 105, 1828; Angew. Chem. Int. Ed. Engl. 1993, 32, 1729. 10 I. Ugi, H. Perlinger, L. Behringer, Chem. Ber. 1958, 91, 2330. 11 During thermal decomposition [Me2GaN(H)Mes]2 reacts under CH activation [19], whereas the corresponding Al compound forms the cubane (MeAlNMes)4. Only when the N atom is coordinated by the sterically more demanding ligand 2,4,6-tBu3C6H2 does the Al compound undergo CH activation [7]. 12 Crystal data of 1: C38H52Al2N2, Mr = 590.78, triclinic, space group P1, a = 1122.5(2), b = 1173.3(2) c = 1370.3(2) pm, α = 92.22(2), β = 109.57(2), γ = 101.25(2), V = 1.6572(5) nm3, Z = 2, ρcalcd = 1.184 Mgm−3; F(000) = 640, λ = 71.073 pm, μ(MoKα) = 0.117 mm−1. The data were collected on a STOE-Siemens-Huber diffractometer. Intensity measurements were performed by 2θ/ω scans in the range 8° ≤ 2θ ≤ 50° at −120°C on a rapidly cooled crystal of dimensions 0.30 × 0.20 × 0.15 mm in an oil drop [20]. Of the 11737 measured reflections, 5869 were independent; largest minimum and maximum in the final difference Fourier synthesis: −345 and 729 enm−3, R1 = 0.0733 (for 3715 reflections with F) > 4σ (F) and wR2 = 0.2004 (all data). 13 The average deviation from the plane is 3.7 pm. 14 Crystal data of 2: C52H96Al4N4Si4, Mr = 997.61, monoclinic, space group P2/c, a = 2516.7(7), b = 1942.8(5) c = 1288.5(4) pm, β = 104.50(3)°, V = 6.099(3) nm3, Z = 4, ρcalcd = 1.086 Mgm−3; F(000) = 2176, λ = 71.073 pm, μ(MoKα) = 0.190 mm−1. The data were collected on a STOE-Siemens-AED diffractometer. Intensity measurements were performed by 2θ/ω scans in the range 8° ≤ 2θ ≤ 45° at −120°C on a rapidly cooled crystal of dimensions 0.45 × 0.25 × 0.20 mm in an oil drop [20]. Of the 7405 measured reflections, 7155 were independent; largest minimum and maximum in the final difference Fourier synthesis: −245 and 237 eÅ−3, R1 = 0.0495 (for 5004 reflections with F>4σ(F)) and wR2 = 0.1181 (all data). The values of R1 and wR2 are defined as R1 = Σ∣F0|–|Fc∣/[Σ|F0|] wR2 = {[Σw(F = F)2]/[Σw(F)2]}1/2. THE structures were solved by direct methods (SHELXS-90) [21] and refined by least-squares against F2 (SHELX-93) [22]. The hydrogen atoms, except the hydrogen atom located on N1 in 1, were positioned geometrically and refined by using a riding model in which the Me groups can rotate about their local axes. The hydrogen atom on N1 in 1 was refined by using distance restraints. Further details of the crystal structure investigations may be obtained from the Director of the Cambridge Crystallographic Data Centre, 12 Union Road, GB-Cambridge CB2 1EZ (UK) on quoting the complete literature citation. 15 G. M. Sheldrick, W. S. Sheldrick, J. Chem. Soc. A 1969, 2279. 16 In both compounds the bond lengths are 178 pm. These are significantly shorter than the sum of the atomic radii (about 200 pm), but correspond well to the value determined according to the equation of Blom and Haaland (179pm) [23]. 17 Power et al. reported the monomeric aminoalane tBu2 AlNRR' whose Al–N bond lengths range between 178 and 189 pm. M. A. Petrie, K. Ruhlandt-Senge, P. P. Power, Inorg. Chem. 1993, 32, 1135. 18 The bond lengths found in iminoalanes with higher degrees of oligomerization range between 189 and 196 pm [4,6]. 19 P. P. Power, J. Organomet. Chem. 1990, 400, 49. 20 T. Kottke, D. Stalke, J. Appl. Crystallogr. 1993, 26, 615. 21 G. M. Sheldrick, Acta Crystallogr. Sect. A 1990, 46, 467. 22 G. M. Sheldrick, SHELXL-93, unpublished results. 23 R. Blom, A. Haaland, J. Mol. Struct. 1985, 129, 21. Citing Literature Volume33, Issue9May 18, 1994Pages 969-970 ReferencesRelatedInformation
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