plays a crucial role on the coordinating ability of the ligand as
well as on the solubility of the resulting nanomaterials. The
most interesting performances in terms of particle size and shape
were obtained with 3,5-disubstituted derivatives. Though many
synthetic approaches toward functional phosphinines have been
devised, most of these studies focused on the elaboration of
2,6-disubstituted derivatives and methods providing a convenient
access toward 3,5-disubstituted compounds have been much less
studied. In most cases, these approaches rely on multistep
procedures that are specific from the nature of the functional
groups grafted at the 3 and 5 positions.15-23 A few years ago
we reported a synthetic strategy, which allows the synthesis of
tetrafunctional derivatives. Polyfunctional compounds,24-27
polydentate ligands,28,29 and phosphorus macrocycles30-33 could
be easily prepared from disubstituted alkynes and 1,3,2-
diazaphosphinine 1 through a cycloaddition/cycloreversion
sequence which is depicted in Scheme 1.
Protodesilylation of 2,6-Disubstituted
Silyphosphinines. Experimental and Theoretical
Study
Matthias Blug, Olivier Piechaczyk, Marie Fustier,
Nicolas Me´zailles, and Pascal Le Floch*
Laboratoire He´te´roe´le´ments et Coordination, Ecole
Polytechnique, CNRS, Palaiseau, France
ReceiVed January 16, 2008
SCHEME 1
However this process could not be successfully extended
toward the synthesis of disubstituted derivatives with terminal
2,6-Disilylphosphinines react with HCl in ethereal solution
to cleanly yield the corresponding 2,6-unsubstituted deriva-
tives. DFT calculations allowed rationalization of the mech-
anism of this protodesilylation.
(13) Moores, A.; Goettmann, F.; Sanchez, C.; Le Floch, P. Chem.
Commun. 2004, 2842-2843.
(14) Goettmann, F.; Moores, A.; Boissiere, C.; Le Floch, P.; Sanchez,
C. Small 2005, 1, 636-639.
(15) Avarvari, N.; Le Floch, P.; Charrier, C.; Mathey, F. Heteroatom
Chem. 1996, 7, 397-402.
Phosphinines1-3 are one of the most important classes of
phosphorus aromatic heterocycles with phospholes4 and their
anionic derivatives. Due to their very specific electronic
properties, that strongly differ from that of classical phosphines
and related nitrogen heterocycles, they have found applications
as ligands in coordination chemistry for the stabilization of
highly reduced complexes5,6 and in homogeneous catalysis such
as the hydroformylation process of olefins.7-12 More recently
they also proved to be well adapted for the growing and
stabilization of metallic nanoparticles.13,14 However, from these
last studies it appeared that the substitution scheme of the ring
(16) Ashe, A. J. J. Am. Chem. Soc. 1971, 93, 3293-3295.
(17) Le Floch, P.; Ricard, L.; Mathey, F. J. Chem. Soc., Chem. Commun.
1993, 789-791.
(18) Ma¨rkl, G.; Matthes, D. Tetrahedron Lett. 1974, 4381-4384.
(19) Ma¨rkl, G.; Adolin, G.; Kees, F.; Zander, G. Tetrahedron Lett. 1977,
3445-3448.
(20) Ma¨rkl, G.; Hock, K.; Merz, L. Chem. Ber.-Recl. 1984, 117, 763-
782.
(21) Keglevich, G.; Ujszaszy, K.; Kovacs, A.; Toke, L. J. Org. Chem.
1993, 58, 977-978.
(22) Ma¨rkl, G.; Hock, K. Tetrahedron Lett. 1983, 24, 2645-2648.
(23) Ma¨rkl, G.; Hock, K.; Matthes, D. Chem. Ber.-Recl. 1983, 116, 445-
472.
(24) Avarvari, N.; Rosa, P.; Mathey, F.; Le Floch, P. J. Organomet.
Chem. 1998, 567, 151-155.
(1) Mathey, F.; Le Floch, P. Sci. Synth. 2005, 15, 1097.
(2) Le Floch, P. Phosphorus-Carbon Heterocyclic Chemistry: The Rise
of a New Domain; Pergamon: New York, 2001; pp 485-534.
(3) Ma¨rkl, G. Multiple Bonds and Low Coordination in Phosphorus
Chemistry; Thieme Verlag: Stuttgart, 1990; pp 220-257.
(4) Quin, L. D. Phosphorus-Carbon Heterocyclic Chemistry: The Rise
of a New Domain; Pergamon: New York, 2001; pp 219-362.
(5) Le Floch, P. Progress in Inorganic Chemistry; John Wiley and
Sons: New York, 2001; Vol. 49.
(25) Avarvari, N.; Le Floch, P.; Ricard, L.; Mathey, F. Organometallics
1997, 16, 4089-4098.
(26) Avarvari, N.; Le Floch, P.; Mathey, F. J. Am. Chem. Soc. 1996,
118, 11978-11979.
(27) Frison, G.; Sevin, A.; Avarvari, N.; Mathey, F.; Le Floch, P. J.
Org. Chem. 1999, 64, 5524-5529.
(28) Sava, X.; Me´zailles, N.; Maigrot, N.; Nief, F.; Ricard, L.; Mathey,
F.; Le Floch, P. Organometallics 1999, 18, 4205-4215.
(29) Me´zailles, N.; Maigrot, N.; Hamon, S.; Ricard, L.; Mathey, F.; Le
Floch, P. J. Org. Chem. 2001, 66, 1054-1056.
(30) Avarvari, N.; Me´zailles, N.; Ricard, L.; Le Floch, P.; Mathey, F.
Science 1998, 280, 1587-1589.
(6) Le Floch, P. Coord. Chem. ReV. 2006, 250, 627-681.
(7) Breit, B. Chem. Commun. 1996, 2071-2072.
(8) Breit, B.; Winde, R.; Harms, K. J. Chem. Soc., Perkin Trans. 1 1997,
2681-2682.
(9) Breit, B.; Winde, R.; Mackewitz, T.; Paciello, R.; Harms, K. Chem.
Eur. J. 2001, 7, 3106-3121.
(31) Avarvari, N.; Maigrot, N.; Ricard, L.; Mathey, F.; Le Floch, P.
Chem.--Eur. J. 1999, 5, 2109-2118.
(10) Moores, A.; Me´zailles, N.; Ricard, L.; Le Floch, P. Organometallics
2005, 24, 508-513.
(32) Me´zailles, N.; Avarvari, N.; Maigrot, N.; Ricard, L.; Mathey, F.;
Le Floch, P.; Cataldo, L.; Berclaz, T.; Geoffroy, M. Angew. Chem., Int.
Ed. 1999, 38, 3194-3197.
(11) Mu¨ller, C.; Vogt, D. Dalton Trans. 2007, 5505-5523.
(12) Mu¨ller, C.; Wasserberg, D.; Weemers, J. J. M.; Pidko, E. A.;
Hoffmann, S.; Lutz, M.; Spek, A. L.; Meskers, S. C. J.; Janssen, R. A. J.;
van Santen, R. A.; Vogt, D. Chem.--Eur. J. 2007, 13, 4548-4559.
(33) Cataldo, L.; Choua, S.; Berclaz, T.; Geoffroy, M.; Me´zailles, N.;
Ricard, L.; Mathey, F.; Le Floch, P. J. Am. Chem. Soc. 2001, 123, 6654-
6661.
10.1021/jo800105b CCC: $40.75 © 2008 American Chemical Society
Published on Web 03/21/2008
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