Chemistry Letters Vol.32, No.10 (2003)
913
NMR was also carried out. In 119Sn NMR there appeared only
one signal for stannole anion 615 at 30.4 ppm with the complete
disappearance of the signal for 3. In 13C NMR a characteristic
low-fielded signal (170.66 ppm) with a large tin–carbon cou-
pling constant of about 113 Hz assignable to the ꢁ-carbon in
6 was observed. In Li NMR a single resonance was observed
at 0.92 ppm, suggesting the the rapid intermolecular exchange
of lithium cations between 6 and lithium chloride.
In summary, stannole dianion 3 was synthesized by reduc-
tion of 1,1,2,3,4,5-hexaphenylstannole 4 with lithium. This is a
convenient method for the synthesis of stannole dianion 3 be-
cause 47 is easily prepared. Reaction of 3 with tert-butyl chlo-
ride gave stannole anion 6, a tin-analogue of cyclopetadienyl
anion. The anion 6 was characterized by 1H, 13C, 119Sn, and
7Li NMR spectra. Further investigation on aromaticity of 6 is
currently in progress.
1553 (1995). b) B. Goldfuss, P. v. R. Schleyer, and F.
Hampel, Organometallics, 15, 1755 (1996). c) B. Goldfuss
and P. v. R. Schleyer, Organometallics, 16, 1543 (1997).
a) M. Saito, M. Nitta, and M. Yoshioka, Organometallics,
20, 749 (2001). b) M. Saito, S. Nakano, and M. Yoshioka,
Tetrahedron Lett., 2001, 7063. c) M. Saito, R. Haga, and
M. Yoshioka, Heteroat. Chem., 15, 349 (2001).
5
7
6
7
M. Saito, R. Haga, and M. Yoshioka, Chem. Commun.,
2002, 1002.
a) W. Z. Rhee and J. J. Zuckerman, J. Am. Chem. Soc., 97,
2291 (1975). b) J. Ferman, J. P. Kakareka, W. T. Klooster, J.
L. Mullin, J. Quattrucci, J. S. Ricci, H. J. Tracy, W. J.
Vining, and S. Wallace, Inorg. Chem., 38, 2464 (1999).
1
8
3: H NMR (400 MHz, ether–C6D6) ꢂ 6.56–6.58 (m, 4H),
6.73–6.74 (m, 6H), 6.80–6.83 (m, 4H), 6.96–6.98 (m, 6H);
13C NMR (101 MHz, ether–C6D6) ꢂ 121.83 (d), 124.01
(d), 126.98 (d), 127.13 (d), 128.53 (d), 132.73 (d), 134.27
(s), 144.12 (s), 150.79 (s), 187.66 (s, JSn-C ¼ 366,
This work was partially supported by Grant-in-Aids for En-
couragement of Young Scientists, Nos. 10740288 (M. S.) and
13740349 (M. S.) from the Ministry of Education, Culture, Sci-
ence, Sports, and Technology, Japan and from Japan Society for
the promotion of Science, respectively. M. Saito also thanks for
research grant for young scientists from Nissan Science Founda-
tion
7
388 Hz); 119Sn NMR (149 MHz, ether–C6D6) ꢂ 131.3; Li
NMR(156 MHz, ether–C6D6) ꢂ ꢁ1:3.
1
9
The J(Sn–C) in ꢁ-carbon of 4 was reported to be 213 and
223 Hz in Ref. 7b.
10 Although monitoring the reaction of 4 with lithium by NMR
in THF–C6D6 also showed the signals assignable to 3 and
phenyllithium, the reaction did not proceed cleanly.
11 7: mp 75–80 ꢂC (decomp)(methylene chloride+methanol).
1H NMR (400 MHz, CDCl3) ꢂ 0.60 (s, 3H), 1.22 (s, 9H),
6.77–6.79 (m, 4H), 6.83–6.85 (m, 4H), 6.93–6.98 (m, 8H),
7.04–7.08 (m, 4H); 13C NMR (101 MHz, CDCl3) ꢂ
ꢁ10:57(q), 29.90(s), 30.68(q), 124.86(d), 125.58(d),
127.18(d), 127.74(d), 129.09(d), 130.44(d), 141.01(s),
143.62(s), 145.41(s), 154.47(s). Anal. Calcd for C33H32Sn:
C, 72.42; H, 5.89. Found: C, 72.43; H, 5.51. The 1J(Sn–
C) in ꢁ-carbon could not be estimated because of broading.
12 M. Wakasa and T. Kugita, Organometallics, 17, 1913
(1998).
References and Notes
1
a) W.-C. Joo, J.-H. Hong, S.-B. Choi, H.-E. Son, and C. H.
Kim, J. Organomet. Chem., 391, 27 (1990). b) J.-H. Hong
and P. Boudjouk, J. Am. Chem. Soc., 115, 5883 (1993). c)
J.-H. Hong, P. Boudjouk, and S. Castellino, Organometal-
lics, 13, 3387 (1994). d) U. Bankwitz, H. Sohn, D. R.
Powell, and R. West, J. Organomet. Chem., 499, C7
(1995). e) R. West, H. Sohn, U. Bankwitz, J. Calabrese,
Y. Apeloig, and T. Mueller, J. Am. Chem. Soc., 117,
11608 (1995). f) W. P. Freeman, T. D. Tilley, G. P. A.
Yap, and A. L. Rheingold, Angew. Chem., Int. Ed. Engl.,
35, 882 (1996). g) W. P. Freeman, T. D. Tilley, L. M.
Liable-Sands, and A. L. Rheingold, J. Am. Chem. Soc.,
118, 10457 (1996).
13 8: mp 270–300 ꢂC (decomp)(recrystallized from methylene
chloride). 1H NMR (400 MHz, CDCl3) ꢂ 1.10 (s, 18H),
6.80–6.84 (m, 8H), 6.87–7.04 (m, 32H); 13C
NMR(101 MHz, CDCl3) ꢂ 31.64(q), 35.21(s), 124.90(d),
125.64(d), 127.20(d), 127.74(d), 129.56(d), 130.65(d),
140.90(s), 143.51(s), 148.46(s), 154.23(s). Anal. Calcd for
C64H58Sn2: C, 72.21; H, 5.49. Found: C, 71.54; H, 5.37.
2
a) P. Dufour, J. Dubac, M. Dartiguenave, and Y.
Dartiguenave, Organometallics, 9, 3001 (1990). b) J.-H.
Hong and P. Boudjouk, Bull. Soc. Chim. Fr., 132, 495
(1995). c) W. P. Freeman, T. D. Tilley, F. P. Arnold, A.
L. Rheingold, and P. K. Gantzel, Angew. Chem., Int. Ed.
Engl., 34, 1887 (1995). d) R. West, H. Sohn, D. R. Powell,
1
The J(Sn–C) in ꢁ-carbon could not be estimated because
of low solubility.
T. Muller, and Y. Apeloig, Angew. Chem., Int. Ed. Engl.,
35, 1002 (1996). e) S.-B. Choi, P. Boudjouk, and J.-H.
Hong, Organometallics, 18, 2919 (1999).
14 N. Wiberg, H. Schuster, A. Simon, and K. Peters, Angew.
Chem., Int. Ed. Engl., 25, 79 (1986).
15 6: H NMR (400 MHz, ether–C6D6) ꢂ 1.25 (s, 9H), 6.61–
¨
1
3
4
For examples of reviews, see: a) E. Colomer, R. J. P. Corriu,
and M. Lheureux, Chem. Rev., 90, 265 (1990). b) J. Dubac,
6.78 (m, 12H), 6.80–6.83 (m, 4H), 6.88–6.90 (m, 4H); 13C
NMR (101 MHz, ether–C6D6) ꢂ 28.64(s), 33.71(q),
122.22(d), 124.04(d), 126.80(d), 127.07(d), 129.35(d),
131.59(d), 145.05(s), 150.35(s), 151.78(s), 170.66 (s,
JSn-C ¼ 113 Hz); 119Sn NMR (149 MHz, ether–C6D6) ꢂ
´
C. Guerin, and P. Meunier, in ‘‘The Chemistry of Organic
Silicon Compounds,’’ ed. by Z. Rappoport and Y. Apeloig,
John Wiley and Sons, Chichester (1998), Vol. 42, p 1961.
a) B. Goldfuss and P. v. R. Schleyer, Organometallics, 14,
7
30.4; Li NMR (156 MHz, ether–C6D6) ꢂ 0.92.
Published on the web (Advance View) September 8, 2003; DOI 10.1246/cl.2003.912