Supporting Information for Angew. Chem. Int. Ed. 200460538 © Wiley-VCH 2004 69451 Weinheim, Germany
Ansa-Cycloheptatrienyl-Cyclopentadienyl Complexes**
Matthias Tamm,* Andreas Kunst, Thomas Bannenberg, Eberhardt Herdtweck, Peter Sirsch, Cornelis J. Elsevier, and Jan M. Ernsting
Contents:
1. Experimental Section 2. Differential Scanning Calorimetry 3. High Pressure NMR study 4. Electronic Structure Calculations 5. Crystal Structure Determinations
2
1. Experimental Section
General: All operations were performed in an atmosphere of dry argon by using Schlenk and vacuum techniques. Solvents were dried by standard methods and distilled prior to use. Troticene has been prepared from [(η-C5H5)TiCl3] and cycloheptatriene according to published procedures.[1] Elemental analyses (C, H, N) were performed on a Elementar Vario EL elemental analyzer. 1H and 13C NMR spectra were measured on Jeol JNM GX 270, Jeol JNM GX 400 or Bruker DPX 400 spectrometers using the solvent as internal standard. The assignment of all resonances was supported by two-dimensional NMR spectroscopy (COSY and COLOC experiments). IR spectra were recorded on a Bio-Rad FTS 575C instrument. UV-vis measurements were carried out on a Varian Cary 50 Scan spectrophotometer using sealed quarz cuvettes.
1: A solution of n-butyllithium (25 mL of a 2.5 M solution in hexane, 62.5 mmol) and of tmeda (73.5 mmol, 11.1 mL) in 80 mL hexane was slowly treated with solid troticene (24.5 mmol, 5.0 g) and stirred overnight. The resulting brownish slurry, containing [(ηC7H6Li)Ti(η-C5H4Li)]·2tmeda,
was
cooled
to
-78
°C,
and
a
solution
of
dichlorodimethylsilane (49.3 mmol, 6.0 mL) in 150 ml hexane was added dropwise over a period of 6 h. The reaction mixture was allowed to reach ambient temperature overnight. After filtration through Celite, the solvent was removed in vacuo. The oily residue was suspended in a few mL of hexane, and the solvent decanted off via a cannula. Drying the residue in high vacuum afforded 1 as a blue-green solid (2.50 g, 39%), which can be purified by crystallization from a thf/hexane mixture at -78°C. 1H NMR (400 MHz, [D6]benzene): δ =
[1] a) H. O. van Oven, H. J. Liefde Meijer, J. Organomet. Chem. 1970, 23, 159-163; b) B. Demerseman, P. H. Dixneuf, J. Douglade, R. Mercier, Inorg. Chem. 1982, 21, 3942-3947.
3
5.89 (m, 4H; C7H6), 4.87 (m, 4H; C5H4), 4.75 (dm, 2H; C7H6), 0.41 (s, 6H; SiCH3). 13
C{H}NMR (100.53 MHz, [D6]benzene): δ = 101.2 (C7H6), 101.0 (C5H4), 100.6 (C5H4), 89.7
(C7H6), 87.6 (C7H6), 83.6 (i-C5H4), 61.6 (i-C7H6), -5.9 (SiCH3). Elemental analysis (%) calcd for C14H16SiTi: C 64.61, H 6.20; found: C 63.44, H 6.49. UV/vis (CH2Cl2): λmax (ε) = 663 (105).
3: A solution of 2,6-dimethylphenylisocyanide (0.69 mmol, 90.7 mg) in 5 mL of THF was added dropwise to a solution of 1 (0.69 mmol, 0.18 g) in 10 mL of THF within 5 min. The brownish reaction mixture was stirred for 15 min and concentrated. Cooling the solution to 78°C yielded red-brown crystal of 3 (0.24 g, 89%). 1H NMR (400 MHz, [D6]benzene): δ = 6.71 (t, 1H; C6H3), 6.57 (d, 2H; C6H3), 5.95 (m, 2H; C7H6), 5.77 (m, 2H; C7H6), 4.96 (m, 2H; C5H4), 4.89 (m, 2H; C5H4), 4.78 (dm, 2H; C7H6), 2.04 (s, 6H; (CCH3), 0.42 (s, 6H; SiCH3). 13
C{H}NMR (100.53 MHz, [D6]benzene): δ = 170.5 (CNR), 134.9 (i-C6H3), 128.5 (C6H3),
128.1 (C6H3), 127.9 (C6H3), 100.3 (C7H6), 100.0 (C5H4), 99.3 (C5H4), 91.1 (C7H6), 88.4 (C7H6), 85.4 (i-C5H4), 63.1 (i-C7H6), 18.6 (CCH3), -5.8 (SiCH3). IR (KBr): 2112 cm-1 (C≡N). Elemental analysis (%) calcd for C23H25NSiTi: C 70.58, H 6.44, N 3.58; found: C 70.13, H 6.70, N 3.50.
4: A solution of 1 (0.77 mmol, 0.20 g) in 10 mL of THF was added dropwise to a solution of tert-butylisocyanide (0.77 mmol, 63.9 mg) in 5 mL of THF within 5min. After stirring for 10min, the resulting brownish solution was concentrated and cooled to -78°C to yield 4 as brownish crystals (0.22 g, 83 %). 1H NMR (400 MHz, [D6]benzene): δ = 5.98 (m, 2H; C7H6), 5.59 (m, 2H; C7H6), 5.10 (m, 2H; C5H4), 4.90 (m, 2H; C5H4), 4.78 (dm, 2H; C7H6), 0.86 (s, 9H; CCH3), 0.41 (s, 6H; SiCH3). 13C{H}NMR (100.53 MHz, [D6]benzene): δ = 100.2 (C7H6), 99.8 (C5H4), 98.7 (C5H4), 91.3 (C7H6), 88.3 (C7H6), 85.4 (i-C5H4), 63.3 (i-C7H6), 53.8
4
(CCH3), 30.5 (CCH3), -5.8 (SiCH3), the CNR resonance could not be observed. IR (KBr): 2153 cm-1 (C≡N). Elemental analysis (%) calcd for C19H25NSiTi: C 66.46, H 7.34, N 4.08; found: C 66.65, H 7.46, N 4.51.
2. Differential Scanning Calorimetry
The DSC study of 1 was performed on a Netzsch STA 409 PC Luxx® calorimeter under argon at a heating rate of 5 K/min in the temperature range of 35 – 220 °C. The sample was prepared under argon using sealable aluminium crucibles (25µL). Internal calibration was performed by measuring the melt enthalpy of Sn, RbNO3, KClO4, Zn and Ag2SO4. A representative DSC thermogram for 1 is shown below.
5
intensity [µV]
0
-5
-10
-15
-20 100
120
140
160
temperature [°C]
180
200
5
3. High Pressure NMR study
Caution: High pressure NMR systems involving pressurized gases (in general and carbon moxide in particular) should be handled according to the appropriate safety measures. The high pressure NMR experiments were carried out in a 10 mm outer diameter, 8 mm inner diameter, sapphire HP-NMR tube with pressure sensor as described previously.[2] Some experiments were performed in a HP-NMR tube similar to the one described by Roe.[3,4] The NMR samples were prepared by charging the HP-NMR tube with about 68 mg of 1 and 1,5 mL of [D8]THF; subsequently it was flushed three times with CO gas and then filled with CO to the desired pressure (between 0 and 60 bar) using a standard gas-supply system. The tube was closed and transferred[4] to the spectrometer that was preset at a temperature between +20 and –70 oC. All spectra were recorded in the standard locked, non-spinning mode.
[2] S. Gaemers, H. Luyten, J. M. Ernsting, C. J. Elsevier, Mag. Res. Chem. 1999, 37, 25-30. [3] D. C. Roe, J. Magn. Res. 1985, 63, 388-391. [4] C. J. Elsevier, J. Mol. Catal. 1994, 92, 285-297.
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4. Electronic Structure Calculations
DFT calculations were carried out with the “Gaussian 03” program suite[5
31]
using the
Becke3LYP density functional[6 32] and the 6-311G(d,p) basis set combination.[7 33] For Ti a slightly modified contraction scheme was used and the basis set was augmented with an additional f-polarization function.[8
34]
All optimizations were performed imposing Cs
symmetry and the resulting geometries were verified as minima on the potential energy surface by computing analytical frequencies.
[5] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. AlLaham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, and J. A. Pople, GAUSSIAN 03, revision B.03, Gaussian, Inc., Pittsburgh PA, 2003. [6] a) A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652; b) C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785-789. [7] a) R. Krishnan, J. S. Binkley R. Seeger, J. A. Pople, J. Chem. Phys. 1980, 72, 650-654; b) A. D. McLean, G. S. Chandler, J. Chem. Phys. 1980, 72, 5639-5648; c) A. J. H. Wachters, J. Chem. Phys. 1970, 52, 10331036. [8] A. W. Ehlers, M. Böhme, S. Dapprich, A. Gobbi, A. Höllwarth, V. Jonas, K. F. Köhler, R. Stegmann, A. Veldkamp, G. Frenking, Chem. Phys. Lett. 1993, 208, 111-114.
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Structure of troticene in cartesian coordinates (atom, x-, y-, z-positions in Å): Ti C C C C C C C C C C C C H H H H H H H H H H H H
-0.001520 -1.208815 -1.638620 -0.374204 -0.374204 0.976076 0.976076 -1.020858 -1.020858 0.366239 0.366239 1.478997 1.478997 -2.288571 -0.707782 -0.707782 1.849626 1.849626 -2.713248 -1.690797 -1.690797 0.604852 0.604852 2.446533 2.446533
0.018013 2.047566 -1.491330 2.047592 2.047592 2.047739 2.047739 -1.492368 -1.492368 -1.490454 -1.490454 -1.485663 -1.485663 2.039990 2.040123 2.040123 2.040151 2.040151 -1.355708 -1.354819 -1.354819 -1.350303 -1.350303 -1.345218 -1.345218
0.000000 0.000000 0.000000 1.148595 -1.148595 0.709861 -0.709861 1.282387 -1.282387 1.598837 -1.598837 0.711819 -0.711819 0.000000 2.175563 -2.175563 1.344479 -1.344479 0.000000 2.122420 -2.122420 2.646183 -2.646183 1.178067 -1.178067
8
Structure of 1 in cartesian coordinates (atom, x-, y-, z-positions in Å): Ti Si C C C C C C C C C C C C C C H H H H H H H H H H H H H H H H
0.256184 -0.381711 1.297930 -1.434500 2.524947 2.524947 -0.974274 -0.974274 1.786892 1.786892 -1.193334 -1.193334 -1.403020 -1.403020 -0.616729 -0.616729 -0.396833 -0.396833 -1.645490 0.047752 0.047752 -1.645490 -1.358526 -1.056701 -0.681839 -0.681839 -1.056701 -1.358526 1.593160 3.015249 3.015249 1.593160
-0.963370 1.992976 1.101610 0.400477 -0.749010 -0.749010 -2.734868 -2.734868 0.381129 0.381129 -1.638706 -1.638706 -0.263393 -0.263393 3.049507 3.049507 2.509874 2.509874 3.416121 3.917923 3.917923 3.416121 0.382084 -1.854052 -3.663942 -3.663942 -1.854052 0.382084 0.636807 -1.472803 -1.472803 0.636807
0.000000 0.000000 0.000000 0.000000 0.710255 -0.710255 0.710668 -0.710668 1.143739 -1.143739 1.585210 -1.585210 1.276428 -1.276428 1.540692 -1.540692 -2.464652 2.464652 1.604629 1.502022 -1.502022 -1.604629 -2.146038 -2.638823 -1.184888 1.184888 2.638823 2.146038 2.175570 1.345704 -1.345704 -2.175570
9
5. Crystal Structure Determinations
a) Crystal structure analysis of compound 1: C14H16SiTi, Mr = 260.23; blue-green fragment (0.20 × 0.30 × 0.36 mm3); orthorhombic, Pnma (No.: 62), a = 7.5213(1), b = 11.8120(2), c = 13.8540(2) Å, V = 1230.81(3) Å3, Z = 4, dcalc = 1.404 gcm-3; F000 = 544; µ = 0.761 mm-1. Preliminary examination and data collection were carried out on a kappa-CCD device (NONIUS MACH3) with an Oxford Cryosystems device at the window of a rotating anode (NONIUS FR591) with graphite monochromated Mo-Kα radiation (λ = 0.71073 Å). Data collection were performed at 123 K within the Θ range of 2.27° < Θ < 25.37°. A total of 23981 reflections were integrated. Raw data were corrected for Lorentz, polarization, and, arising from the scaling procedure, for latent decay and absorption effects. After merging (Rint = 0.071), 1183 [1117: Io>2σ(Io)] independent reflections remained and all were used to refine 111 parameters. The structure was solved by a combination of direct methods and differenceFourier syntheses. All non-hydrogen atoms were refined with anisotropic displacement parameters. All hydrogen atoms were found and refined with individual isotropic displacement parameters. Full-matrix least-squares refinements were carried out by minimizing Σw(Fo2-Fc2)2 and converged with R1 = 0.0390 [Io>2σ(Io)], wR2 = 0.0865 [all data], GOF = 1.200, and shift/error < 0.001. The final difference-Fourier map shows no striking features (∆emin/max = +0.54/-0.23 eÅ-3). b) Crystal structure analysis of compound 4: C19H25NSiTi, Mr = 343.36; brownish plate (0.13 × 0.56 × 0.91 mm3); monoclinic, P21/c (No.: 14), a = 8.2062(1), b = 20.0538(2), c = 11.6431(2) Å, β = 104.5477(5)°, V = 1854.62(4) Å3, Z = 4, dcalc = 1.230 gcm-3; F000 = 728; µ = 0.523 mm-1. Preliminary examination and data collection were carried out on a kappa-CCD device (NONIUS MACH3) with an Oxford Cryosystems device at the window of a rotating anode (NONIUS FR591) with graphite monochromated Mo-Kα radiation (λ = 0.71073 Å).
10
Data collection were performed at 173 K within the Θ range of 2.07° < Θ < 25.34°. A total of 40934 reflections were integrated. Raw data were corrected for Lorentz, polarization, and, arising from the scaling procedure, for latent decay and absorption effects. After merging (Rint = 0.068), 3373 [3042: Io>2σ(Io)] independent reflections remained and all were used to refine 297 parameters. The structure was solved by a combination of direct methods and differenceFourier syntheses. All non-hydrogen atoms were refined with anisotropic displacement parameters. All hydrogen atoms were found and refined with individual isotropic displacement parameters. Full-matrix least-squares refinements were carried out by minimizing Σw(Fo2-Fc2)2 and converged with R1 = 0.0390 [Io>2σ(Io)], wR2 = 0.0787 [all data], GOF = 1.175, and shift/error < 0.001. The final difference-Fourier map shows no striking features (∆emin/max = +0.29/-0.19 eÅ-3). The tert.-butyl group appeared to be disordered (0.65(1) : 0.35(1)) over two positions. 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-237472 (1) and CCDC-237473 (4). Copies of the data can be obtained free of charge on application to CCDC, 12
Union
Road,
Cambridge
CB2
1EZ,
UK
(fax:
(+44)1223-336-033;
e-mail:
[email protected]). c) Data Collection Software for Nonius kappa-CCD devices, Delft (The Netherlands), 2001; d) Z. Otwinowski, W. Minor, Methods in Enzymology 1997, 276, 307ff; e) A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, M. C. Burla, G. Polidori, M. Camalli, SIR92, J. Appl. Crystallogr. 1994, 27, 435-436; f) International Tables for Crystallography, Vol. C, Tables 6.1.1.4, 4.2.6.8, and 4.2.4.2 (ed.: A. J. C. Wilson), Kluwer Academic Publishers, Dordrecht (The Netherlands), 1992; g) A. L. Spek, PLATON, A Multipurpose Crystallographic Tool, Utrecht University, Utrecht (The Netherlands), 2001; h) G. M. Sheldrick, SHELXL-97, Universität Göttingen, Göttingen (Germany), 1998.
