2322
S.G.A. van Assema et al. / Journal of Organometallic Chemistry 692 (2007) 2314–2323
(d) L. Maurette, C. Tedeschi, E. Sermot, M. Soleilhavoup, F.
Hussain, B. Donnadieu, R. Chauvin, Tetrahedron 60 (2004) 10077–
10098, and references cited therein;
4.11. P(CBC–TES)2(CBC–TMS) (19b)
Phosphine (11b) (0.1 mmol) was reacted with HCl(g)/
Et2O and BrMg–CBC–TMS to give trisethynylphosphine
(19b) in analogy to the procedure described above for
19a. The reaction was followed by 31P NMR and showed
that chlorophosphine (18b) (d31P 16.1) is cleanly converted
to 19b. Rapid filtration over silica gel resulted in partial
conversion to the phosphine oxide 20b (d31P (hexane)
À57.4). Filtration of the mixture (19b and 20b) over
Al2O3 enabled the isolation of 19b. 31P NMR (CDCl3)
d = À88.5 (s); 1H NMR (CDCl3) d = 0.2 (s, 9H; Si(CH3)3),
(e) F. Maraval, R. Chauvin, Chem. Rev. 106 (2006) 5317–7343.
[5] (a) K.N. Houk, L.T. Scott, N.G. Rondan, D.C. Spellmeyer, G.
Reinhardt, J.L. Hyun, G.J. DeCicco, R. Weiss, M.H.M. Chen, L.S.
Bass, J. Clardy, F.S. Jorgensen, T.A. Eaton, V. Sarkozi, C.M. Petit,
L. Ng, K.D. Jordan, J. Am. Chem. Soc. 107 (1985) 6556–6562;
(b) H. Jiao, N.J.R.v. Eikema Hommes, P.v.R. Schleyer, A. de
Meijere, J. Org. Chem. 61 (1996) 2826–2828;
(c) C. Lepetit, B. Silvi, R. Chauvin, J. Phys. Chem. A 107 (2003) 464–
473;
(d) D.B. Werz, R. Gleiter, Org. Lett. 6 (2004) 589–592.
[6] L.T. Scott, M.J.M. Cooney, in: P.J. Stang, F. Diederich (Eds.),
Modern Acetylene Chemistry, VCH, Weinheim, 1995, pp. 321–351
(Chapter 9).
3
3
0.64 (q, J(H,H) = 7.8 Hz; SiCH2CH3), 1.02 (t, J(H,H) =
7.8 Hz; SiCH2CH3).
´
[7] R.M. Gonzalez, Ph.D. Thesis (with L.T. Scott), University of
Nevada, Reno, NV, 1993.
[8] (a) M. Unno, T. Saito, H. Matsumoto, Bull. Chem. Soc. Jpn. 74
(2001) 2407–2413, and references cited therein;
Acknowledgements
(b) M. Unno, T. Saito, H. Matsumoto, Chem. Lett. (1999) 1235–
1236;
(c) M. Voronkov, O. Yarosh, G. Turkina, V. Vitkovskii, A. Albanov,
J. Organomet. Chem. 389 (1990) 1–22;
(d) M.G. Voronkov, L.V. Zhilitskaya, O.G. Yarosh, T.D. Burnash-
ova, A.I. Albanov, L.V. Klyba, Russ. J. Gen. Chem. 71 (2001) 537–
539;
This work was supported by the Council for Chemical
Sciences of the Netherlands Organization for Scientific Re-
search (NWO/CW). We thank Prof. L.T. Scott of Boston
College for insightful information.
(e) E. Hengge, A. Baumegger, J. Organomet. Chem. 369 (1989) C39–
C42.
Appendix A. Supplementary material
[9] K.D. Dillon, F. Mathey, J.F. Nixon, Phosphorus: The Carbon Copy,
Wiley, Chichester, 1998.
[10] L.T. Scott, M. Unno, J. Am. Chem. Soc. 112 (1990) 7823–7825.
[11] M.J. Cooney, Cyclic Homoconjugated Polyacetylenes, Ph.D. Thesis
(with L.T. Scott), University of Nevada, Reno, NV, 1993, pp. 176–
180 (Chapter 4).
˚
Cartesian coordinates (A) and energies (a.u.) of all sta-
tionary points and NMR spectral data. Supplementary
data associated with this article can be found, in the online
[12] R. Shiozawa, K. Sakamoto, Chem. Lett. 32 (2003) 1024–1025.
[13] G. Ma¨rkl, T. Zollitsch, P. Kreitmeier, M. Prinzhorn, S. Reithinger,
E. Eibler, Chem. Eur. J. 6 (2000) 3806–3920.
References
[1] (a) F. Diederich, Pure Appl. Chem. 77 (2005) 1851–1863;
(b) M.B. Nielsen, F. Diederich, Chem. Rev. 2 (2002) 189–198;
(c) M.B. Nielsen, N.F. Utesch, N.N. Moonen, C. Bouden, J.P.
Gisselbrecht, S. Concilio, S.P. Piotto, P. Seiler, P. Gunter, M. Gross,
F. Diederich, Chem. Eur. J. 8 (2002) 3601–3618;
(d) M.B. Nielsen, F. Diederich, Synlett 4 (2002) 544–552.
[2] (a) A.M. Boldi, F. Diederich, Angew. Chem., Int. Ed. Engl. 33 (1994)
468–471;
[14] (a) C. Charrier, W. Chodkiewicz, P. Cadiot, Bull. Soc. Chim. Fr. 3
(1966) 1002–1011;
(b) A.J. Carty, N.K. Hota, T.W. Ng, H.A. Patel, T.J. O’Connor,
Can. J. Chem. (1971) 2706–2711;
(c) W.E. Davidsohn, M.C. Henry, Chem. Rev. 67 (1967) 73–106;
(d) P. Bharathi, M. Periasamy, Organometallics 19 (2000) 5511–5513.
[15] (a) I.P. Beletskaya, V.V. Afanasiev, M.A. Kazankova, I.V. Efimova,
Org. Lett. 5 (2003) 4309–4311;
Angew. Chem. 106 (1994) 482–485;
(b) L. Gobbi, P. Seiler, F. Diederich, Angew. Chem., Int. Ed. Engl.
38 (1999) 674–678;
(b) V.V. Afanasiev, I.P. Beletskaya, M.A. Kazankova, I.V. Efimova,
M.U. Antipin, Synthesis (2003) 2835–2838.
[16] P. Manini, W. Amrein, V. Gramlich, F. Diederich, Angew. Chem.,
Int. Ed. 41 (2002) 4339–4343;
Angew. Chem. 111 (1999) 737–740;
(c) F. Diederich, Chem. Commun. (2001) 219–227;
(d) P. Siemsen, R.C. Livingston, F. Diederich, Angew. Chem., Int.
Ed. 39 (2000) 2632–2657;
Angew. Chem. 114 (2002) 4515–4519.
[17] S.G.A. van Assema, G.B. de Jong, A.W. Ehlers, F.J.J. de Kanter, M.
Schakel, A.L. Spek, M. Lutz, K. Lammertsma, Eur. J. Org. Chem.
Angew. Chem. 112 (2000) 2740–2767;
(e) M.B. Nielsen, M. Schreiber, Y.G. Baek, P. Seiler, S. Lecomte, C.
Boudon, R.R. Tykwinski, J.P. Gisselbrecht, V. Gramlich, P.J.
Skinner, C. Bosshard, P. Gunter, M. Gross, F. Diederich, Chem.
Eur. J. 7 (2001) 3263–3280.
[18] A. Ochida, H. Ito, M. Sawamura, J. Am. Chem. Soc. (2006). ASAP;
and references cited therein.
[19] A procedure for complexing other phosphines with W(CO)5 was
followed: A. Marinetti, S. Bauer, L. Ricard, F. Mathey, Organomet-
allics 9 (1990) 793–798.
[3] (a) L.T. Scott, G.J. DeCicco, J.L. Hyunn, G. Reinhardt, J. Am.
Chem. Soc. 105 (1983) 7760–7761;
[20] (a) T. Imamoto, F. Oshiki, T. Onozawa, T. Kusumoto, K. Sato, J.
Am. Chem. Soc. 112 (1990) 5244–5252;
(b) L.T. Scott, G.J. DeCicco, J.L. Hyunn, G. Reinhardt, J. Am.
Chem. Soc. 107 (1985) 6546–6555.
(b) A. Borner, J. Ward, W. Ruth, J. Holz, A. Kless, D. Heller, H.B.
¨
[4] (a) L.T. Scott, M.J. Cooney, D.W. Rogers, K. Dejroongruang, J.
Am. Chem. Soc. 110 (1988) 7244–7245;
Kagan, Tetrahedron 50 (1994) 10419–10430.
[21] (a) Stable ethynylphosphine-boranes are known: J. Bould, R.
Greatrex, J.D. Kennedy, D.L. Ormsby, M.G.S. Londesborough,
K.L.F. Callaghan, M. Thornton-Pett, T.R. Spalding, S.J. Teat, W.
Clegg, H. Fang, N.P. Rath, L. Barton, J. Am. Chem. Soc. 124 (2002)
7429–7439;
(b) A. de Meijere, S. Kozhushkov, T. Haumann, R. Boese, C. Plus,
M.J. Cooney, L.T. Scott, Chem. Eur. J. 1 (1995) 124–131;
(c) R. Boese, A.J. Matzger, K.P.C. Vollhardt, J. Am. Chem. Soc. 119
(1997) 2052–2053;