10.1002/chem.201604892
Chemistry - A European Journal
An excess of HSiCl3 (0.25 g, 1.81 mmol) was added to a stirred solution of ligand L2
(0.15 g, 0.36 mmol) in toluene (20 mL). The reaction mixture was stirred overnight.
After that all volatiles were removed under reduced pressure to give 5 as white solid of
m.p. = 217-219 °. Yield: 0.15 g (83%). Anal. calcd. for C30H24Cl2N2Si (MW 511.52): C
[4] B. Marciniec, in Hydrosilylation: A Comprehensive Review on Recent Advances,
Springer, Springer Netherlands, 2009. DOI 10.1007/978-1-4020-8172-9
[5] a) W. E. Piers, A. J. V. Marwitz, L. G. Mercier, Inorg. Chem. 2011, 50, 12252–
12262; b) J. M. Blackwell, E. R. Sonmor, T. Scoccitti, W. E. Piers, Org. Lett. 2000,
2, 3921–3923.
1
70.4; H 4.7. Found: C 70.5; H 4.9. H NMR (C6D6, 500.20 MHz): 4.05 (bs, 2H, CH2N),
5.78 (d, 1H, py-H, 3J(1H, 1H) = 7.8 Hz), 6.00 (s, 1H, Si-H, 1J(29Si, 1H) = 369 Hz), 6.07 (t,
1H, py-H, 3J(1H, 1H) = 6.5 Hz), 6.39 (t, 1H, py-H, , 3J(1H, 1H) = 7.6 Hz), 7.02 – 7.71 (m,
17H, ArH), 8.15 (bs, 1H, py-H); 13C NMR (C6D6, 125.72 MHz): 49.6 (CH2N), 123.5,
126.7, 126.9, 128.0, 128.2, 128.7, 128.9, 129.3, 129.6, 134.4, 134.9, 140.1, 140.4, 142.4,
154.8 (Ar-C); 29Si NMR (C6D6, 99.36 MHz): -95.6 (d, 1J(29Si-1H) 369 Hz).
[6] a) P. A. Chase, T. Jurca, D. W. Stephan, Chem. Commun. 2008, 1701–1703; b) D.
Chen, J. Klankermayer, Chem. Commun. 2008, 2130–2131; c) P. Spies, S.
Schwendemann, S. Lange, G. Kehr, R. Frçhlich, G. Erker, Angew. Chem. 2008,
120, 7654 – 7657; Angew. Chem. Int. Ed. 2008, 47, 7543–7546; d) V. Sumerin, F.
Schulz, M. Atsumi, C. Wang, M. Nieger, M. Leskel_, T. Repo, P. Pyykkö, B.
Rieger, J. Am. Chem. Soc. 2008, 130, 14117–14119; e) K. Chernichenko, M.
Nieger, M. Leskel, T. Repo, Dalton Trans. 2012, 41, 9029–9032.
Alternative synthesis of 5. A solution of 2 (0.98 g, 1.81 mmol) in toluene (15 mL) was
added to a solution of HSiCl3 (0.25 g, 1.81 mmol) in toluene (15 mL) at room
temperature. After stirring for 12 hours, the reaction mixture was filtrated. From the
filtrate compound 5 precipitated as single crystalline material suitable for X-ray
diffraction analysis as toluene solvate 5.½C7H8.
[7] For reviews on imine reductions, see: a) S. Kobayashi, H. Ishitani, Chem. Rev.
1999, 99, 1069–1094; b) R. O. Hutchins, M. K. Hutchins, in Comprehensive
Organic Synthesis, Vol. 8 (Eds: B. M. Trost, I. Fleming), PERGAMON PRESS,
New York, 1991, p 25. For proposed intermediacy of silyliminium cations, see: a)
Jahangir, D. B. MacLean, M. A. Brook, H. L. Holland, J. Chem. Soc., Chem.
Commun. 1986, 1608–1609; b) M. Johannsen, K. A. Jorgensen, G. Helmchen, J.
Crystallography: The single crystals suitable for X-ray diffraction analysis were
obtained from saturated toluene solution at room temperature (1, 5.½C7H8) or at 4 °C
(4.C7H8). The single crystals of 3 suitable for X-ray diffraction analysis were obtained
from C6D6 solution at room temperature. Crystal structure analysis of colourless crystal
of 1·(0.25 x 0.12 x 0.11 mm3), yellow of 3·(0.37 x 0.23 x 0.19 mm3), colourless of
4.C7H8 (0.37 x 0.32 x 0.26 mm3) and of 5.½C7H8 (0.31 x 0.22 x 0.21 mm3) were
obtained at 150K using Oxford Cryostream low-temperature device on a Nonius
Am. Chem. Soc. 1998, 120, 7637–7638. For
a proposed stannyliminium
KappaCCD diffractometer with Mo K radiation (
= 0.71073 Å), a graphite
intermediate, see: T. Suwa, I. Shibata, K. Nishino, A. Baba, Org. Lett. 1999, 1,
1579–1581.
monochromator, and the and scan mode. Data reductions were performed with
DENZO-SMN[22]. The absorption was corrected by integration methods.[23] Structures
were solved by direct methods (Sir92)[24] and refined by full matrix least-square based
on F2 (SHELXL97)[25] Hydrogen atoms were mostly localized on a difference Fourier
map, however to ensure uniformity of treatment of crystal, all hydrogen were
recalculated into idealized positions (riding model) and assigned temperature factors
Hiso(H) = 1.2 Ueq(pivot atom) or of 1.5Ueq for the methyl moiety with C-H = 0.96, 0.97,
and 0.93 Å for methyl, methylene, and hydrogen atoms in aromatic ring, respectively.
There are residual electron maxima within the unit cell probably originated from the
disordered solvent in the structure of 5. PLATON /SQUEZZE[26] was used to correct the
data for the presence of disordered solvent. A potential solvent volume of 598 Ǻ3 was
found. 124 electrons per unit cell worth of scattering were located in the void. The
calculated stoichiometry of solvent was calculated to be two molecules of toluene per
unit cell which results in 100 electrons per unit cell.
[8] a) D. J. Parks, J. M. Blackwell, W. E. Piers, J. Org. Chem. 2000, 65, 3090–3098;
b) S. Rendler, M. Oestreich, Angew. Chem. 2008, 120, 6086 – 6089; Angew. Chem.
Int. Ed. 2008, 47, 5997–6000; c) J. M. Blackwell, E. R. Sonmor, T. Scoccitti, W. E.
Piers Org. Lett, 2000, 2, 3921 – 3923.
[9] a) J. Fassler, S. Bienz, Organometallics 1994, 13, 4704-4707; b) R. J. P. Corriu, G.
F. Lanneau, M. Perrot, Tetrahedron Lett. 1987, 28, 3941-3944; c) M. Yamamura,
N. Kano, T. Kawashima, Tetrahedron Lett. 2007, 48, 4033-4036; d) K. Lippe, D.
Gerlach, E. Kroke, J. Wagler, Organometallics 2009, 28, 621-629; e) M.
Yamamura, N. Kano, T. Kawashima, Z. Anorg. Allg. Chem. 2009, 635, 1295-1299;
f) S. Anwar, A. P. Davis, J. Chem. Soc., Chem. Commun. 1986, 831-832; g) S. W.
McCombie, C. Ortiz, B. Cox, A. K. Ganguly, Synlett 1993, 541-547.
Crystallographic data for structural analysis have been deposited with the Cambridge
Crystallographic Data Centre, CCDC nos. 1431188-1431190 (1, 3 and 4) and CCDC no
1454048 (5) contain the supplementary crystallographic data for this paper. These data
can be obtained free of charge from The Cambridge Crystallographic Data Centre via
[10] For recent reviews on hypercoordinate silicon compounds see: a) V. A.
Pestunovich, S. Kirpichenko, M. G. Voronkov, in The Chemistry of Organic
Silicon Compounds, Vol. 2 (Eds: Y. Apeloig, Z. Rappoport), Wiley: Chichester,
U.K., 1998, p 1447-1537; b) C. Chuit, R.J.P. Corriu, C. Reyé. in Chemistry of
HyperValent Compounds, (Ed: K. Akiba), Wiley-VCH: Weinheim, Germany,
1999, p 81-146; c) R. Tacke, M. Pülm, B. Wagner, Adv. Organomet. Chem. 1999,
44, 221–273; d) M. A. Brook, Silicon in Organic, Organometallic and Polymer
Chemistry; Wiley: New York, 2000, p 97-141; e) R. Tacke, O. Seiler, in Silicon
Chemistry: From the Atom to Extended Systems, (Eds: P. Jutzi, U. Schubert),
Wiley-VCH: Weinheim, Germany, 2003, p 324-337; f) D. Kost, I. Kalikhman, in
The Chemistry of Organic Silicon Compounds, Vol. 2 (Eds: Y. Apeloig, Z.
Supporting Information. Crystallographic parameters of compounds 1, 3, 4.C7H8 and
5.½C7H8. Experimental details and NMR spectra for the synthesis of the unsymmetrical
amines. Calculated coordinates of 1, 1a_1, 1a_2 and Int_1 and Int_2. Optimized
geometry of complex 1. Calculated energies of 1, 1a_1 and 1a_2 as well as Int_1 and
Int_2.
Rappoport), Wiley: Chichester, U.K., 1998,
p 1339- 1445; g) D. Kost, I.
Kalikhman, Adv. Organomet. Chem. 2004, 5, 1–106; h) A. R. Bassindale, S. J.
Glynn, P. G. Taylor, in The Chemistry of Organic Silicon Compounds, Vol. 2,
(Eds: Y. Apeloig, Z. Rappoport), Wiley: Chichester, U.K., 1998, p 495-511.
Acknowledgements
We are grateful to the Czech Science Foundation (project no. P207/13-00289S) for
supporting this work.
[11] a) R. J. P. Corriu, J. C. Young, in The Chemistry of Organic Silicon Compounds,
(Eds: S. Patai, Z. Rappoport), Wiley: New York, 1989, p 1241-1288; b) R. J. P.
Corriu,G. F. Lanneau, Y. Zhifang, Tetrahedron 1993, 49, 9019–9030; c) R. J. P.
Corriu, G. F. Lanneau, M. Perrot-Petta, V.D. Mehta, Tetrahedron Lett. 1990, 31,
2585–2588; d) J. Boyer, C. Breliere, R. J. P. Corriu, A. Kpoton, M. Poirier, G.
Royo, J. Organomet. Chem. 1986, 311, C39-C43; e) R. J. P. Corriu, G. F. Lanneau,
M. Perrot, Tetrahedron Lett. 1988, 29, 1271 -1274; f) P. Arya, R. J. P. Corriu, K.
Gupta, G. F. Lanneau, Z. Yu, J. Organomet. Chem. 1990, 399, 11-33; g) R. J. P.
Corriu, G. F. Lanneau, M. Perrot-Petta, V. D. Nehta, Tetrahedron Lett. 1990, 31,
2585-2588; h) R. J. P. Corriu, G. F. Lanneau, Z. Yu, Tetrahedron 1993, 49, 9019-
9030; i) Y. Domoto, A. Fukushima, Y. Kasuga, S. Sase, K. Goto, T. Kawashima,
Org. Lett. 2010, 12, 2586-2589.
[1] a) I. Ojima, in The Chemistry of Organic Silicon Compounds, (Eds: S. Patai, Z.
Rappoport), John Wiley, Chichester, 1989,
p 1479; b) B. Marciniec, in
Comprehensive Handbook on Hydrosilylation, Pergamon, New York, 1992; c) T.
Hiyama, T. Kusumoto, in Comprehensive Organic Synthesis, Vol. 8, (Eds: B. M.
Trost, I. Fleming) Pergamon Press, Oxford, 1991, p 763; d) S. H. Bergens, P.
Noheda, J. Whelan, B. Bosnich, J. Am. Chem. Soc. 1992, 114, 2121–2128; e) I.
Ojima, K. Hirai, in Asymmetric Synthesis, Vol. 5 (Eds: J. D. Morrison),
Academic Press, New York, 1985, p 103; f) H. B. Kagan, J. F. Peyronel, T.
Yamagishi, in Adv. in Chemistry Series: Inorganic Compounds with Unusual
Properties-II, Vol. 173, (Eds: R. B. King), Americam Chemical Society,
Washington, DC, 1979, p 50;
[12] a) E. Kertsnus-Banchik, I. Kalikhman, B. Gostevskii, Z. Deutsch, M. Botoshansky,
D. Kost, Organometallics 2008, 27, 5285–5294; b) N. Kano, K. Yanaizumi, X.
Meng, N. Havare, T. Kawashima, Chem. Commun. 2013, 49, 10373–10375; c) K.
Lippe, D. Gerlach, E. Kroke, J. Wagler, Organometallics, 2009, 28, 621–629; d)
G. W. Fester, J. Eckstein, D. Gerlach, J. Wagler, E. Brendler, E. Kroke, Inorg.
Chem, 2010, 49, 2667–2673;.
[2] For examples of hydrosilylation reactions catalysed by transition metals see for
example: a) A. Monney, M. Albrecht, Chem. Commun. 2012, 48, 10960–10962; b)
W. Sattler, G. Parkin, J. Am. Chem. Soc. 2012, 134, 17462–17465; c) C. L. C.
Misal, H. Li, J.-P. Sortais, Ch. Darcel, Chem. Commun. 2012, 48, 10514–10516; d)
A. Hojilla, C. Crisita, A. M. Tondreau, K. J. Weller, K. M. Lewis, R. W. Cruse, S.
A. Nye, J. L. Boyer, J. G. P. Delis, P. J. Chirik, ACS Catal. 2012, 2, 2169–2172; e)
Ch. Cheng, M. Brookhart, J. Am. Chem. Soc., 2012, 134, 11304–11307.
[13] a) M. Novák, L. Dostál, M. Alonso, F. De Proft, A. Růžička, A. Lyčka, R. Jambor,
Chem. Eur. J. 2014, 20, 2542–2550; b) M. Novák, L. Dostál, J. Turek, M. Alonso,
F. De Proft, A. Růžička, R. Jambor, Chem. Eur. J. 2016, 22, 5620–5628; c) L.
Witteman, T. Evers, Z. Shu, M. Lutz, R. J. M. Klein Gebbink, M.-E. Moret, Chem.
Eur. J. 2016, 22, 6087-6099; d) H. Hošnová, M. Novák, L. Dostál, Z. Růžičková,
R. Jambor, Inorg. Chim. Acta. 2016, 453, 457-462.; e) A. Kämpfe, E. Brendler, E.
Kroke, J. Wagler, Chem. Eur. J. 2014, 20, 9409–9418.
[3] a) J. Boyer, C. Breliere, R. J. P. Corriu, A. Kpoton, M. Poirier, G. Royo, J.
Organomet. Chem. 1986, 311, C39–C43; b) R. J. P. Corriu, R. Perz, C. Reye,
Tetrahedron 1983, 39, 999–1009; c) R. Calas, Pure Appl. Chem. 1966, 13, 61–80;
d) J. L. Fry, M. Orfanopoulo, M. G. Adlington, W. R. Dittman, S. B. Silverman, J.
Org. Chem.1978, 43, 374–375; e) M. P. Doyle, C. T. West, S. J. Donnelly, C. C.
McOsker, J. Organomet. Chem. 1976, 117, 129–140.
7
This article is protected by copyright. All rights reserved.