Synthesis and Structure Determination of Bicyclic [Li(tmeda)] 2 [S 6 ]
1990; Wiley; Volume: 29; Issue: 4 Linguagem: Inglês
10.1002/anie.199004221
ISSN1521-3773
AutoresKazuyuki Tatsumi, Yoshihisa Inoue, Akira Nakamura, Roger E. Cramer, William VanDoorne, John W. Gilje,
Tópico(s)Synthesis and characterization of novel inorganic/organometallic compounds
ResumoAngewandte Chemie International Edition in EnglishVolume 29, Issue 4 p. 422-424 Communication Synthesis and Structure Determination of Bicyclic [Li(tmeda)]2[S6]† Dr. Kazuyuki Tatsumi, Corresponding Author Dr. Kazuyuki Tatsumi Department of Macromolecular Science, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan) Kazuyuki Tatsumi, Department of Macromolecular Science, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan) Akira Nakamura, Department of Macromolecular Science, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan) Roger E. Cramer, Department of Chemistry, University of Hawaii Honolulu. HI 96822 (USA)Search for more papers by this authorYoshihisa Inoue, Yoshihisa Inoue Department of Macromolecular Science, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan)Search for more papers by this authorDr. Akira Nakamura, Corresponding Author Dr. Akira Nakamura Department of Macromolecular Science, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan) Kazuyuki Tatsumi, Department of Macromolecular Science, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan) Akira Nakamura, Department of Macromolecular Science, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan) Roger E. Cramer, Department of Chemistry, University of Hawaii Honolulu. HI 96822 (USA)Search for more papers by this authorProf. Dr. Roger E. Cramer, Corresponding Author Prof. Dr. Roger E. Cramer Department of Chemistry, University of Hawaii Honolulu. HI 96822 (USA) Kazuyuki Tatsumi, Department of Macromolecular Science, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan) Akira Nakamura, Department of Macromolecular Science, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan) Roger E. Cramer, Department of Chemistry, University of Hawaii Honolulu. HI 96822 (USA)Search for more papers by this authorProf. Dr. William VanDoorne, Prof. Dr. William VanDoorne Department of Chemistry, University of Hawaii Honolulu. HI 96822 (USA)Search for more papers by this authorProf. Dr. John W. Gilje, Prof. Dr. John W. Gilje Department of Chemistry, University of Hawaii Honolulu. HI 96822 (USA)Search for more papers by this author Dr. Kazuyuki Tatsumi, Corresponding Author Dr. Kazuyuki Tatsumi Department of Macromolecular Science, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan) Kazuyuki Tatsumi, Department of Macromolecular Science, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan) Akira Nakamura, Department of Macromolecular Science, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan) Roger E. Cramer, Department of Chemistry, University of Hawaii Honolulu. HI 96822 (USA)Search for more papers by this authorYoshihisa Inoue, Yoshihisa Inoue Department of Macromolecular Science, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan)Search for more papers by this authorDr. Akira Nakamura, Corresponding Author Dr. Akira Nakamura Department of Macromolecular Science, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan) Kazuyuki Tatsumi, Department of Macromolecular Science, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan) Akira Nakamura, Department of Macromolecular Science, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan) Roger E. Cramer, Department of Chemistry, University of Hawaii Honolulu. HI 96822 (USA)Search for more papers by this authorProf. Dr. Roger E. Cramer, Corresponding Author Prof. Dr. Roger E. Cramer Department of Chemistry, University of Hawaii Honolulu. HI 96822 (USA) Kazuyuki Tatsumi, Department of Macromolecular Science, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan) Akira Nakamura, Department of Macromolecular Science, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan) Roger E. Cramer, Department of Chemistry, University of Hawaii Honolulu. HI 96822 (USA)Search for more papers by this authorProf. Dr. William VanDoorne, Prof. Dr. William VanDoorne Department of Chemistry, University of Hawaii Honolulu. HI 96822 (USA)Search for more papers by this authorProf. Dr. John W. Gilje, Prof. Dr. John W. Gilje Department of Chemistry, University of Hawaii Honolulu. HI 96822 (USA)Search for more papers by this author First published: April 1990 https://doi.org/10.1002/anie.199004221Citations: 12 † This work was supported by the National Science Foundation (Grant CHE 85-19289 for R. E. C. and J. W. C.) and by the donors of the Petroleum Research Fund administered by the American Chemical Society. 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 Li2S6 system of the bicycle[4.1.1] type is the distinctive feature of the title compound 1. The corresponding "nucleus" is depicted in the illustration to the right, in which the two tetramethylenediamine ligands are not fully drawn. No such structures have so far been observed for other alkali metal, alkaline earth, or transition metal polysulfides. References 1 J. R. Birk, R. K. Steunenberg Adv. Chem. Scr. 140 (1975) 186. and references therein. 2(a) According to phase diagram studies Li2S3 or Li2S4 may be a stable species above 360 °C: P. T. Cunningham, S. A. Johnson, E. J. Cairns, J. Electrochem. Soc. 119 (1972) 1448; (b) R. A. Sharma, E. J. Cairns, J. Electrochem. Soc. 119 (1972) 1439. 3(a) D.-G. Oei, Inorg. Chem. 12 (1973) 435, 438; (b) L. S. Marcoux, E. T. Seo Adv. Chem. Ser. 140 (1975) 216. 4(a) R. Tegman, Acta Crysiallogr. Sec. B: Struct. Crystallogr. Cryst. Chem. 29 (1973) 1463; (b) B. Kelly, P. Woodward, J. Chem. Soc. Daltan Trans, 1976, 1314; (c) S. C. Abrahams, J. L. Bernstein, Acta Crysiallogr. Sec, B: Siruct. Crystallogr. Cryst. Chem, 25 (1969) 2365; (d) S. C. Abrahams, E. Grison, Acta Crystallogr, 6 (1953) 206; (e) A. Hordvik, E. Stetten, Atca Chem. Scand. 22 (1968) 3029. 5(a) (Ph4P)2S7 and TI2S2 contain ionic acyclic polysulfides as well. Cf. M. G. Kanalzidis, N. C. Baenzigcr, D. Coucouvanis, Inorg. Chem. 22 (1983) 290; (b) B. Leclerc, T. S. Kabré, Acta Crystallogr. Sec. B: Struct. Crystallogr. Cryst. Chem. 31 (1975) 1675. 6 A single crystal of 1 was mounted in a glass capillary and sealed under argon. Crystal size 0.7 × 0.5 × 0.2 mm, monoclinic, space group C2/c, a = 22.808(4), b = 9.194(1), c = 15.038(2)Å = 129.80(1)°, Qcalcd = 1.48 g cm−3, Z = 4. μ(Moka) = 5.13 cm−1. X-ray data were collected on a Nicolet p3 diffractometer in the θ/2θ mode using graphilc-moncxhromated MoKa radiation. The data were corrected for Lorcntz and polarization effects, and an empirical absorption correction was applied. The 931 observed reflections with F > 3.0 σ(F) from 1255 measured reflections were used for the structure determination. The structure was solved by direct methods and the subsequent full-matrix least squares refinements gave final R values of R = 0.0463 and RG = 0.0444. The inner four sulfur atoms of the S6, unit, of which two are related to the other two by a crystallographically imposed C2 axis, were found to be disordered with 0.591 (9)/0.409(9) occupancy factors (x/y scries). GOF = 1.81, Δ/σ = 0.49. (ϱ)max. = 0.20 c Å−3, Ne/Nv = 8.8. All computations with a Nicolet SHELXTL PLUS package with micro VAX II. Further details of the crystal structure analysis can be obtained from the Fachinformalions zentrum Karlsruhe, Gesellschaft für wissenschaftlich-technische Information mbH, D-7514 Eggenstein-Leopoldshafcn 2 (FRG), by quoting the depository number CSD-54331. the names of the authors, and the journal citation. 7 M. Draganjac, T. B. Rauchfuss, Angew. Chem. 97 (1985) 745; Angew. Chem. Int. Ed. Engl. 24 (1985) 742. and references therein. 8 D. Coucouvanis, P. R. Patil, M. G. Kanatzidis, B. Dctcring, N. C. Bacnziger, Inorg. Chem. 24 (1985) 24. 9(a) E. Weiss, U. Joergens, Chem. Ber. 105 (1972) 481; (b) R. Amstutz, D. Seebach, P. Seiler, B. Achwcizer, J. Dunitz, Angew. Chem. 92 (1980) 59; Angew. Chem. Int. Ed. Engl. 19 (1980) 53; (b) K. Tatsumi, I. Maisubara, Y. Inoue, A. Nakamura, R. E. Cramer, G. J. Tagoshi, J. A. Golen, J. W. Gilje. Unpublished; (c) K. Tatsumi, Y. Inoue, A. Nakamura, R. E. Cramer, W. VanDoorne, J. W. Gilje, J. Am. Chem. Soc. 111 (1989) 782. 10(a) H. H. Eysel, G. Wieghardt, H. Kleinschmager, G. Weddingen, Z. Naturforsch. B 31 (1976) 415; (b) F. P. Daly, C. W. Brown, J. Phys. Chem 79 (1975) 350; (c) G. J. Janz, E. Roduner, J. W. Coults, J. R. Downey, Jr. Inorg. Chem. 15 (1976) 1751; (d) G. J. Janz, J. W. Coutts, J. R. Downey. Jr., E. Roduner, Inorg. Chem. 15 (1976) 1755; (e) G. J. Janz, J. R. Downey. Jr., G. J. Wasilezyk, J. W. Coutts, A. Eluard, Inorg. Chem. 15 (1976) 1759; (f) Ii Ziemann, W. Bues, Z. Anorg. Allg. Chem. 455 (1979) 69. 11(a) D. W. Scott,.T. P. McCullough, J. Mol. Spectrosc. 13 (1964) 313; (b) R. Steudel, H.-J. Mäusle, Z. Naturforsch. A 33 (1978) 951. and references therein. 12 Lithium polysulfides in liquid ammonia have recently been characterized by Raman and UV/VIS spcclroscopy; suggest existence of Li2S2 Li2S4 Li2S6 and Li2S6 in addition to S and probably Li2, S. Interestingly, the least reduced polysulfide in the solution was claimed to be S: P. Dubois, J. P. Lelicur, G. Lepoutre, Inorg. Chem. 27 (1988) 73. 13 For example, the size of the polysulfide ring in the (C3H3)2MSx and (C5Me5MSx) systems seems to depend on the organometal fragment x = 5 for (C5H5)2M (M = Ti. Zr. Hf, V) and (C5Mc3),Th. x = 4 for, (C5H5)2Mo and (C5H5)2W, x = 3 for (C5Me5)2Ti: E. Samuel, Bull. Soc Chim. Fr. 1966, 2548; M. Schmidt, B. Block, H. D. Block, H Köpf, E. Wilhelm, Angew. Chem. 80 (1968) 660; Angew. Chem. Int. Ed. Engl. (1968) 632; E. F. Epstein, I. Bernal, H. Kopf, J. Organtimet. Chem 20 (1971) 229; E. G. Müller, J. L. Petcrscn, L. F. Dahl, J. Organtimet. Chem 111 (1976) 91 J. M. McCail, A. Shaver, J. Organtimet. Chem 193 (1980) C37; H. Köpf, Angew. Chem. 8, (1969) 332; Angew. Chem. Int. Ed. Engl. 8 (1969) 375; B. R. Davis, I. Bernal, H. Köpf, Angew. Chem. Int. Ed. Engl. 83 (1971) 1018 and Angew. Chem. Int. Ed. Engl. 10 (1971) 921; P. H. Bird, J. M. McCall, A. Shaver, U. Siriwadane, Angew. Chem. Int. Ed. Engl. 94 (1982) 375 and Angew. Chem. Int. Ed. Engl. 21 (1982) 384; D. A. Wrobleski, D. T. Cramer, J. V. Ortiz, T. B. Rauchfuss, R. R. Ryan, A. P. Sattelberger, J. Am. Chem. Soc. 108 (1986) 174. 14 'Li2S2' was prepared as light yellow powder by reaction of lithium metal and elemental sulfur (1:1) in liquid ammonia. According to the Raman spectra, this material is nearly identical with that prepared from LiEt3 BH('superhydride') and 1/8 S8, and presumably contains small quantities of other lithium sulfides, e. g., Li2S3, Li2S4, as well as S8, Disproportionation might occur in THF, and in view of the dark color, the sulfur content in the THF washings is probably higher than the original Li2S2 stoichiometry. The other polysuilfides Li2 Sx (x = 3–6) were also prepared in liquid ammonia. 15 (a) All manipulations were carried out under argon using dry solvents (b)Addition of tmeda directly to a slurry of 'Li2S2' in toluene followed by standard work-up furnished crystals of 1 was obtained from Li2Sx (x = 3–6)+ tmeda systems as well. 1H NMR of 1 (100MHz, C6 D6, Room Temperature) δ = 2.00 (s, 4H, CH2), 2.18 (s, 12H, CH3). (c) The 1H-NMR spectrum of free tmeda (neat) shows two singlets at δ = 2.39(CH2)and 2.26 (CH3). 16(a) R. Bonnaterre, G. Cauquis, J. Chem. Soc. Chem, Commun, 1972, 293; (b) D. M. Gruea, R. L. McBeth, A. J. Zielen, J. Am. Chem. Soc. 93 (1971) 6691. Citing Literature Volume29, Issue4April 1990Pages 422-424 ReferencesRelatedInformation
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