A stable distannirane

Article abstract of DOI:10.1021/ja0464239

The first three-membered ring compound containing two tin and one carbon atoms, 1,1,2,2-tetra(2,4,6-triisopropylphenyl)-3-fluorenylidene-1,2-distannirane, has been synthesized in a two-step procedure from the 9-[bis(2,4,6-triisopropylphenyl)fluorostannyl]chloromethylenefluorene. Copyright

Full text of DOI:10.1021/ja0464239

Published on Web 09/03/2004
A Stable Distannirane
Lise Baiget, Henri Ranaivonjatovo, Jean Escudie´,* and Heinz Gornitzka
UniVersite´ Paul Sabatier, He´te´rochimie Fondamentale et Applique´e, UMR 5069, 118 route de Narbonne,
31062 Toulouse Cedex 04, France
Received June 17, 2004; E-mail: escudie@chimie.ups-tlse.fr
Three-membered heterocycles comprising a main group element
are important compounds that have attracted large interest. This is
mainly due to their particular structure and to the strain of the cycle
conferring great reactivity on them, which makes them interesting
building blocks in organic and organometallic chemistry.
The synthesis of heavy analogues of cyclopropanes I-III (Chart
1) has been a great challenge for the last few years. Silicon and
germanium heterocycles I(ab), II(ab), and III(ab) have been
reported.1 Going down the periodic table, the stabilization of three-
membered heterocycles becomes more and more difficult. Thus,
in the case of tin, all efforts to prepare I(c)2a and II(c) have been
unsuccessful thus far, and only the symmetrical III(c)2b-d has been
synthesized.
in the reaction (reaction of t-BuCl with t-BuLi). Both compounds
1 and 4 were isolated in pure form by fractional crystallization.
The molecular structure of 1 in the solid state is shown in Figure
1. The red crystals of 1 are thermally stable and can be handled in
air, at least for a short time, and solutions of 1 in usual organic
solvents show no change after two weeks. Such stability of this
highly strained heterocycle displaying extremely acute angles on
tin and carbon atoms in the three-membered ring (50.7(3)°, 51.3(3)°,
and 78.2(4)°, respectively) is very surprising; it is probably due to
the large steric protection provided by the Tip groups.
Chart 1
We present in this communication the synthesis in a two-step
procedure of the first three-membered heterocycle of type II(c)
containing two tin and one carbon atoms, 1,1,2,2-tetra(2,4,6-tri-
isopropylphenyl)-3-fluorenylidene-1,2-distannirane 1.
Figure 1. Structure of 1. Ellipsoids are drawn at 50% probability level.
iPr groups are simplified for clarity. Selected bond lengths (Å) and angles
(deg): Sn1-Sn2 2.777(2), Sn1-C1 2.209(12), Sn2-C1 2.196(12), C1-
C2 1.360(16), Sn1-Sn2-C1 51.1(3), Sn2-C1-Sn1 78.2(4), C1-Sn1-
Sn2 50.7(3).
The first step of the synthesis of 1 involved the preparation of
4
stannylalkene 23 by addition of Tip2SnF2 (Tip ) 2,4,6-triisopro-
pylphenyl) to a THF solution of the carbenoid ClC(Li)dCR2 (CR2
5
) fluorenylidene) obtained from Cl2CdCR2 and n-butyllithium
The endo- and exocyclic Sn-C bond lengths (2.17-2.21 Å) lie
in the normal range.8 The Sn-Sn bond length (2.777(2) Å) is
significantly shorter than in other three- or four-membered ring
compounds of tin9 substituted by the same Tip groups; for example,
2.827(1) Å in a telluradistannirane SnSnTe,10a 2.942 Å in (Tip2Sn)3,10b
2.840(1) Å in a 1,2-distannacyclobutene,10c and 2.889(1) Å in a
1,2-dithiadistannetane SnSnSS.10d
(eq 1). The structure of 2 was confirmed by an X-ray analysis (see
Supporting Information), which displays standard bond lengths and
angles and deserves no special comments.
Especially interesting is the environment of the tin atoms: the
sums of the bond angles at tin ignoring C1 are 354 and 352.3°;
thus, the four ipso carbons of the Tip groups and the two tin atoms
lie almost in the same plane. This nearly planar bonding geometry
is in remarkable agreement with that found for a closely related
disilirane SiSiC with an exocyclic CdC double bond11a and a
digermirane GeGeC.11b Similar planar structures were found in other
types of three-membered heterocycles containing two Ge, Sn, or
Si atoms and a heteroelement such as SnSnX (X ) N,9 Te10a),
GeGeX (X ) N,11b S,11c Te11d) and SiSiX compounds (X ) O,11e
S,11f Se11g).
Addition of 1 equiv of tert-butyllithium to 2 afforded distannirane
16 and the 9-[bis(2,4,6-triisopropylphenyl)chlorostannyl]chloro-
methylenefluorene 47 as a byproduct (eq 2); the formation of the
latter is explained by a F/Cl exchange between 2 and LiCl formed
The above results were interpreted in terms of the Dewar-
Chatt-Duncanson model of metal olefin bonding.12 In our case,
the short Sn-Sn bond and the almost planarity of Sn atoms also
suggest that the bonding in 1 may be intermediate between that in
a normal three-membered ring and that of a π-complex (Chart 2).
9
11792
J. AM. CHEM. SOC. 2004, 126, 11792-11793
10.1021/ja0464239 CCC: $27.50 © 2004 American Chemical Society

C O M M U N I C A T I O N S
Chart 2
(2) (a) A stannirene Sn-CdC has been synthesized by cycloaddition between
a stannylene and an alkyne: Sita, L. R.; Bickerstaff, R. D. J. Am. Chem.
Soc. 1988, 110, 5208. (b) Masamune, S.; Sita, L. J. Am. Chem. Soc. 1985,
107, 6390. (c) Sita, L. R.; Kinoshita, I. Organometallics 1990, 9, 2865.
(d) Fu, J.; Neumann, W. P. J. Organomet. Chem. 1984, 272, C5.
(3) 119Sn NMR δ: -117.2 (d, 1J(119SnF) ) 2451.3 Hz); 19F NMR δ: -105.1,
1J(117SnF) ) 2343.9 Hz, 1J(119SnF) ) 2451.3 Hz.
(4) Anselme G.; Ranaivonjatovo, H.; Escudie´, J.; Couret, C. Organometallics
1992, 11, 2748.
(5) Rezaei, H.; Normant, J. F. Synthesis 2000, 1, 109.
The reaction mechanism leading to the distannirane 1 is not clear
at the moment. One of the possible routes to 1 involves the initial
formation of the transient stannaallene 3 according to Scheme 1,
(6) A volume of 1.26 mL (1.88 mmol) of t-BuLi (1.5 M in pentane) was
added dropwise to a solution of Tip2Sn(F)C(Cl)dCR2 (1.36 g, 1.80 mmol)
in THF (25 mL) cooled to -78 °C. The reaction mixture turned red, was
stirred for half an hour at this temperature, and then allowed to warm to
room temperature. After 30 min of stirring, solvents were removed under
vacuum, 20 mL of pentane was added, and the lithium salts were removed
by filtration. Fractional crystallizations from pentane afforded 0.36 g (33%)
Scheme 1
1
of 1 as red crystals (mp 185 °C). H NMR δ (300 MHz): 0.74 and 0.75
3
3
(2d, JHH ) 6.6 Hz, 2 × 24H, o-Me Tip); 1.11 (d, JHH ) 6.9 Hz, 24H,
3
p-Me Tip); 2.73 (sept, JHH ) 6.9 Hz, 4H, p-CH(Me)2 Tip); 3.08 (sept,
3JHH ) 6.6 Hz, 8H, o-CH(Me)2 Tip); 6.83 (s, 4JSnH ) 17.7 Hz, 8H, m-CH
Tip); 6.96 and 7.17 (2t, 3JHH ) 7.2 Hz, 2 × 2H, HCbCg and HCcCf); 7.56
and 7.57 (2d, JHH ) 7.2 Hz, 2 × 2H, HCaCh and HCdCe). 13C NMR δ
3
(75.47 MHz): 24.03 and 24.12 (p-Me Tip); 24.71 and 25.61 (o-Me Tip);
34.28 (5JSnC ) 9.3 Hz, p-CH(Me)2 Tip); 39.38 (4JSnC ) 19.4 Hz, 3JSnC
)
36.1 Hz, o-CH(Me)2 Tip); 118.97 (CdCe); 121.85 (3JSnC ) 35.1 Hz, m-C
Tip); 122.51, 126.92, and 127.80 (Ca-c, Cf-h); 139.71, 140.37, and 143.27
(JSnC ) 23.7 Hz) (CjCk, ClCm, and ipso-C Tip); 149.65 (p-C Tip); 151.29
(CdC); 154.83 (2JSnC ) 39.4 Hz, o-C Tip); 166.78 (CdC). 119Sn NMR
δ: -365.3, 1J(119Sn117Sn) ) 4673.8 Hz. MS (DCI/NH3, m/z, %): 1260
(M + N2H7 - 1, 100); 1244 (M + NH4, 7); 1227 (M + 1, 8); 1056 (M
+ N2H7 - Tip - 2, 26); 1040 (M + NH4 - Tip - 1, 3); 1024 (M + 1
- Tip, 3). Anal. Calcd for C74H100Sn2: C, 72.44; H, 8.21. Found: C,
72.35; H, 8.40. A total of 0.44 g of byproduct 4 was also isolated.
(7) 119Sn NMR δ: -112.9. 4 has been obtained by an independent synthesis
from R2CdC(Li)Cl and Tip2SnCl2.
(8) Standard d(Sn-C): 2.15-2.21 Å. (a) Charissse, M.; Roller, S.; Dra¨ger,
M. J. Organomet. Chem. 1992, 427, 23. (b) Samuel-Lewis, A.; Smith, P.
J.; Aupeas, J. H.; Hampson, D.; Povey, D. C. J. Organomet. Chem. 1992,
437, 131. (c) Bochkarev, L. N.; Grachev, O. V.; Zillsov, S. F.; Zakharov,
L. N.; Struchkov, Y. T. J. Organomet. Chem. 1992, 436, 299. (d) Cardin,
C. J.; Cardin, D. J.; Convery, M. A.; Devereux, M. M. J. Organomet.
Chem. 1991, 411, C3. (e) Weidenbruch, M.; Scha¨fers, K.; Schlaefke, J.;
Peters, K.; Von Schnering, H. G. J. Organomet. Chem. 1991, 415, 343.
(f) Weidenbruch, M.; Scha¨fer, A.; Kilian, H.; Pohl, S.; Saak, W.;
Marsmann, H. Chem. Ber. 1992, 125, 563.
(9) The Sn-Sn bond is shorter (2.709(2) Å) in the azadistanniridine SnSnN
with tin atoms substituted by 2,4,6-(CF3)3C6H2 groups: Gru¨tzmacher, H.;
Pritzkow, H. Angew. Chem., Int. Ed. Engl. 1991, 30, 1017.
(10) (a) Scha¨fer, A.; Weidenbruch, M.; Saak, W.; Pohl, S.; Marsmann, H.
Angew. Chem., Int. Ed. Engl. 1991, 30, 834. (b) Brady, F. J.; Cardin, C.
J.; Cardin D. J.; Convery, M. A.; Devereux, M. M.; Lawless, G. A. J.
Organomet. Chem. 1991, 241, 199. (c) Weidenbruch, M.; Scha¨fer, A.;
Kilian, H.; Pohl, S.; Saak, W.; Marsmann, H. Chem. Ber. 1992, 125, 563.
(d) Scha¨fer, A.; Weidenbruch, M.; Saak, W.; Pohl, S.; Marsmann, H.
Angew. Chem., Int. Ed. Engl. 1991, 30, 962.
13
since the germaallene Tbt(Mes)GedCdCR2 (Tbt ) 2,4,6-tris-
[bis(trimethylsilyl)methyl]phenyl) has been obtained by a similar
procedure from Tbt(Mes)Ge(Cl)-C(Cl)dCR2 and tert-butyllithium.
More generally, E(X)-C(Cl)dE′ (E, E′ ) Si, Ge, P, As) systems
are good precursors of heteroallenes.14 Stannaallene 3, because of
the probable lability of the tin-carbon double bond, could behave
as a stannylene-carbene complex as observed in the related
stannaketenimine R2SndCdNMes (R
) 2,4,6-tris(trifluoro-
methyl)phenyl) that behaves as stannylene R2Sn and isocyanide
CdNMes in reactions with trapping agents;15 thus, a [2 + 1]
cycloaddition between 3 and the stannylene Tip2Sn: should lead
to 1.
Similar formations of three-membered ring derivatives from
doubly bonded tin compounds have been previously reported: a
distannagermirane SnSnGe was obtained by a similar [2 + 1]
cycloaddition between a germastannene >SndGe< and a stannyl-
ene,16 an azadistanniridine SnSnN between a stannaimine >SndN-
and a stannylene,9 and a tristannirane between a stannylene and a
distannene.8f Thus, the postulated mechanism to obtain 1 could
constitute the first evidence for the formation of a transient stanna-
allene still unknown, whereas its lighter analogues >MdCdC<
(M ) Si,17 Ge13,18) have been isolated.
(11) (a) Ishikawa, M.; Sigisawa, H.; Kumada, M.; Higuchi, T.; Matsui, K.;
Hirotsu, K.; Iyoda, J. Organometallics 1983, 2, 174. (b) Tsumuraya, T.;
Sato, S.; Ando, W. Organometallics 1990, 9, 2061. (c) Tsumuraya, T.;
Sato, S.; Ando, W. Organometallics 1988, 7, 2015. (d) Tsumuraya, T.;
Kabe, Y.; Ando, W. J. Chem. Soc., Chem. Commun. 1990, 1159. (e)
Yokelson, H. B.; Millevolte, A. J.; Gillette, G. R.; West, R. J. Am. Chem.
Soc. 1987, 109, 6865. (f) Nicolaou, K. C.; Kwang, C.-K.; Duggan, M.
E.; Carroll, P. J. J. Am. Chem. Soc. 1987, 109, 3801. (g) Tan, P. P.-K.;
Gillette, G. R.; Powell, D. R.; West, R. Organometallics 1991, 10, 546.
(12) (a) Dewar, M. J. S. Bull. Soc. Chim. Fr. 1951, 18, C71. (b) Chatt, J.;
Duncanson, L. A. J. Chem. Soc. 1953, 2939.
The study of the chemical reactivity of distannirane 1 and the
use of bulkier groups on the tin atom to stabilize the hypothetical
stannaallenic intermediate are now under active investigation.
Supporting Information Available: X-ray structural information
on 1 and 2 (CIF, ORTEP view of 2) and experimental details of the
preparation of 1, 2, and 4 and their physicochemical data. This material
is available free of charge via the Internet at http://pubs.acs.org.
(13) Tokitoh, N.; Kishikawa, K.; Okazaki, R. Chem. Lett. 1998, 811.
(14) For reviews on heteroallenes, see: (a) Escudie´, J.; Ranaivonjatovo, H.;
Rigon, L. Chem. ReV. 2000, 100, 3639. (b) Eichler, B.; West, R. AdV.
Organomet. Chem. 2001, 46, 1.
(15) Gru¨tzmacher, H.; Freitag, S.; Herbst-Irmer, R.; Sheldrick, G. S. Angew.
Chem., Int. Ed. Engl. 1992, 31, 437.
(16) Chaubon, M. A.; Escudie´, J.; Ranaivonjatovo, H.; Satge´, J. Chem.
Commun. 1996, 2621.
References
(17) (a) Miracle, G.; Ball, J. L.; Powell, D. R.; West, R. J. Am. Chem. Soc.
1993, 115, 11598. (b) Trommer, M.; Miracle, G. E.; Eichler, B. E.; Powell,
D. R.; West, R. Organometallics 1997, 16, 5737. (c) Eichler, B. E.;
Miracle, G. E.; Powell, D. R.; West, R. Main Group Met. Chem. 1999,
22, 147.
(1) For reviews on small heterocycles of group 14 elements, see: (a) Kabe,
Y.; Ando, W. AdV. Strain Org. Chem. 1993, 3, 59. (b) Ando, W.; Kabe,
Y.; Nami, C. Main Group Met. Chem. 1994, 17, 209. (c) Weidenbruch,
M. Chem. ReV. 1995, 95, 1479. (d) Ando, W.; Kabe, Y. In The Chemistry
of Organic Silicon Compounds; Rappoport, Z., Apeloig, Y., Eds.; Wiley:
Chichester, U.K., 1988; Vol. 2, Part 3, Chapter 42.
(18) Eichler, B. E.; Powell, D. R.; West, R. Organometallics 1999, 18, 540.
JA0464239
9
J. AM. CHEM. SOC. VOL. 126, NO. 38, 2004 11793