9 M. Appel, S. Blaurock and S. Berger, Eur. J. Org. Chem., 2002, 1143.
10 T. Kawashima, K. Kato and R. Okazaki, J. Am. Chem. Soc., 1992,
114, 4008–4010.
11 T. Kawashima, H. Takami and R. Okazaki, J. Am. Chem. Soc.,
1994, 116, 4509–4510.
12 A. S. Ionkin, W. J. Marshall, B. M. Fish, M. F. Schiffhauer and
F. Davidson, J. Am. Chem. Soc., 2007, 129, 9210–9215.
13 F. Volatron and O. Eisenstein, J. Am. Chem. Soc., 1987, 109, 1–14.
14 V. K. Aggarwal, R. Robiette, J. Richardson and J. N. Harvey,
J. Am. Chem. Soc., 2005, 127, 13468–13469.
Scheme 3 Reaction of 2 with triphenylphosphine oxide; NMR yield
is quoted against C6Me6 as an internal standard (average of three
experiments).
15 V. K. Aggarwal, R. Robiette, J. Richardson and J. N. Harvey,
J. Am. Chem. Soc., 2006, 128, 2394–2409.
16 M. Schlosser and H. B. Tuong, Angew. Chem., Int. Ed. Engl., 1979,
18, 633.
17 R. A. Neumann and S. Berger, Eur. J. Org. Chem., 1998,
1085–1087.
18 M. Schlosser, Angew. Chem., Int. Ed. Engl., 1968, 7, 650.
19 A. B. Reitz, S. O. Nortey, A. D. Jordan, M. S. Mutter and
B. E. Maryanoff, J. Org. Chem., 1986, 51, 3302–3308.
20 W. J. Ward Jr. and W. E. McEwen, J. Org. Chem., 1990, 55,
493.
21 M. Schlosser, H. B. Tuong and C. Tarchini, Chimia, 1977, 31, 219.
22 M. Schlosser, A. Piskala, C. Tarchini and H. Batuong, Chimia,
1975, 29, 341–342.
Scheme 4 Reversibility in the Wittig-olefination of 2; NMR yields
23 U. Schroder and S. Berger, Eur. J. Org. Chem., 2000, 2601–2604.
24 M. Schlosser and K. F. Christma, Angew. Chem., Int. Ed. Engl.,
1964, 3, 636.
¨
are quoted against C6Me6 as an internal standard.
In both instances significant cross-over was observed suggesting
reversible C–C s-bond formation (Scheme 4).2,52
25 C. Geletneky, F.-H. Forsterling, W. Bock and S. Berger, Chem.
¨
Ber., 1993, 126, 2397–2401.
We have reported the synthesis of an yttrium phosphonium
ylide adduct and its reaction with benzophenone to form a
hydrocarbon soluble metal-coordinated betaine (the C–C s-bond
formation step of the Wittig reaction under salt conditions). Upon
addition of triphenylphosphine oxide to 2 C–C p-bond formation is
observed. We are continuing to study this system and the reaction
chemistry of onium ylides coordinated to electrophilic metal centres
and will report our findings in subsequent publications.
26 P. L. Watson and G. W. Parshall, Acc. Chem. Res., 1985, 18,
51–56.
27 P. L. Watson, J. Chem. Soc., Chem. Commun., 1983, 276.
28 H. Schumann, I. Albrecht, F. W. Reier and E. Hahn, Angew.
Chem., Int. Ed. Engl., 1984, 23, 522–523.
29 H. Schumann and F. W. Reier, J. Organomet. Chem., 1981,
209, C10.
30 H. Schumann and F. W. Reier, J. Organomet. Chem., 1982,
235, 287.
31 H. Schumann, F. W. Reier and M. Dettlaff, J. Organomet. Chem.,
1983, 255, 305–310.
32 H. Schumann and F. W. Reier, J. Organomet. Chem., 1984, 269,
21–27.
M.R.C is indebted to the Royal Society for the provision of
a University Research Fellowship.
33 H. Schmidbaur, Angew. Chem., Int. Ed. Engl., 1983, 22, 907–927.
34 H. Schmidbaur, Acc. Chem. Res., 1975, 8, 62–70.
35 L. E. Manzer, Inorg. Chem., 1976, 15, 2567–2569.
36 P. Berno, S. Gambarotta, S. Kotila and G. Erker, Chem. Commun.,
1996, 779–780.
37 R. Fandos, M. Gomez, P. Royo, S. Garciablanco, S. Martinezcarrera
and J. Sanzaparicio, Organometallics, 1987, 6, 1581–1583.
38 P. L. Arnold and I. J. Casely, Chem. Rev., 2009, 109, 3599–3611.
39 W. Fegler, T. P. Spaniol and J. Okuda, Dalton Trans., 2010, 39,
6774–6779.
40 J. C. J. Bart, J. Chem. Soc. B, 1969, 350.
41 W.-K. Wong, J. Guan, J. Ren and Q. Shen, Polyhedron, 1993, 12,
2749–2751.
42 W.-K. Wong, J. Guan, Q. Shen, L. Zhang and Y. Lin, Polyhedron,
1995, 14, 277–283.
43 P. L. Arnold, Z. R. Turner, R. Bellabarba and R. P. Tooze, J. Am.
Chem. Soc., 2011, 133, 11744–11756.
44 Z. R. Turner, R. Bellabarba, R. P. Tooze and P. L. Arnold, J. Am.
Chem. Soc., 2010, 132, 4050–4051.
45 Y. Yang, D. M. Cui and X. S. Chen, Dalton Trans., 2010, 39, 3959.
46 Y. Nakajima and J. Okuda, Organometallics, 2007, 26, 1270–1278.
47 A. Bondi, J. Phys. Chem., 1964, 68, 441–451.
48 D. J. Mindiola and J. Scott, Nat. Chem., 2011, 3, 15–17.
49 D. P. Mills, L. Soutar, W. Lewis, A. J. Blake and S. T. Liddle,
J. Am. Chem. Soc., 2010, 132, 14379–14381.
Notes and references
z Crystal data for 2: C44H63IN2OPSi4Y, M = 995.10, monoclinic,
P21/n (no. 14), a = 12.5750(4), b = 24.9990(7), c = 15.7491(4) A, b =
91.687(3)1, V = 4948.8(2) A3, Z = 4, Dc = 1.336 g cmꢀ3, m(Mo-Ka) =
1.964 mmꢀ1, T = 173 K, colourless needles, Oxford Diffraction
Xcalibur 3 diffractometer; 15 749 independent measured reflections
(Rint = 0.0293), F2 refinement, R1(obs) = 0.0359, wR2(all) = 0.0787,
11 490 independent observed absorption corrected reflections
[|Fo| 4 4s(|Fo|), 2y max = 641], 487 parameters. CCDC 843184.
y Crystal data for 1: C31H53IN2PSi4Y, M = 812.89, monoclinic, P21/n
(no. 14), a = 8.8866(18), b = 12.252(3), c = 36.576(7) A, b =
92.160(4)1, V = 3979.4(14) A3, Z = 4, Dc = 1.357 g cmꢀ3, m(Mo-Ka) =
2.423 mmꢀ1, T = 150 K, colourless needles, Bruker SMART APEX
CCD diffractometer; 9304 independent measured reflections (Rint =
0.0981), F2 refinement, R1(obs) = 0.0558, wR2(all) = 0.1604. CCDC
843183.
1 E. Vedejs and C. F. Marth, J. Am. Chem. Soc., 1990, 112, 3905–3909.
2 E. Vedejs, G. P. Meier and K. A. J. Snoble, J. Am. Chem. Soc.,
1981, 103, 2823–2831.
3 E. Vedejs and K. A. J. Snoble, J. Am. Chem. Soc., 1973, 95, 5778–5780.
4 A. B. Reitz, M. S. Mutter and B. E. Maryanoff, J. Am. Chem. Soc.,
1984, 106, 1873–1875.
5 F. Ramirez, C. P. Smith and J. F. Pilot, J. Am. Chem. Soc., 1968,
90, 6726–6732.
6 R. W. Saalfrank, W. Paul and H. Liebenow, Angew. Chem., Int.
Ed. Engl., 1980, 19, 713–714.
50 M. Fustier, X. F. Le Goff, P. Le Floch and N. Mezailles, J. Am.
Chem. Soc., 2010, 132, 13108–13110.
51 R. Litlabo, M. Zimmermann, K. Saliu, J. Takats, K. W. Tornroos
and R. Anwander, Angew. Chem., Int. Ed., 2008, 47, 9560–9564.
52 M. Schlosser and K. F. Christmann, Angew. Chem., Int. Ed. Engl.,
1965, 4, 689.
7 H. J. Bestmann, K. Roth, E. Wilhelm, R. Bohme and H. Burzlaff,
Angew. Chem., Int. Ed. Engl., 1979, 18, 876–877.
8 G. H. Birum and C. N. Matthews, Chem. Commun., 1967, 137.
c
This journal is The Royal Society of Chemistry 2012
Chem. Commun., 2012, 48, 1745–1747 1747