R. Bertani et al. / Journal of Organometallic Chemistry 642 (2002) 32–39
39
[
[
4] T.W. Hanks, P.W. Jennings, J. Am. Chem. Soc. 109 (1987) 5023.
5] R. Bertani, R.A. Michelin, M. Mozzon, P. Traldi, M.F.C.
Guedes da Silva, A.J.L. Pombeiro, Organometallics 14 (1995)
dicationic complex cis-[Pt(PPh ) (CH CN) ][BF ] (2)
3
2
3
2
4 2
was previously reported to catalyze the formation of
the corresponding olefin [10]. The dicationic complexes
have been shown to be efficient catalysts in the cyclo-
propanation of styrene with EDA and in the insertion
of carbenes derived either from DAF or EDA in the
OꢁH bond of alcohols to give ethers. These latter
reactions generally proceed under milder conditions
and with higher yields than those reported for platinu-
m(II) complexes [3]. As a matter of fact, using DAF as
the carbene precursor and the neutral complex cis-
5
51.
[
[
6] S. Boverie, F. Simal, A. Demonceau, A.F. Noels, I.L. Eremenko,
A.A. Sidorov, S.E. Nefedov, Tetrahedron Lett. 38 (1997) 7543.
7] R. Bertani, R.A. Michelin, M. Mozzon, P. Traldi, R. Seraglia, L.
Busetto, M.C. Cassani, P. Tagliatesta, G. D’Arcangelo,
Organometallics 16 (1997) 3229.
[
[
8] M.F.C. Guedes da Silva, J.J.R. Frausto da Silva, A.J.L.
Pombeiro, R. Bertani, R.A. Michelin, M. Mozzon, F. Benetollo,
G. Bombieri, Inorg. Chim. Acta 214 (1993) 85.
9] (a) Y. Kataoka, O. Matsumoto, M. Ohashi, T. Yamagata, K.
Tani, Chem. Lett. (1994) 1283;
[
PtCl (PPh ) ] we did not observe any insertion into the
2 3 2
(
(
b) Y. Kataoka, O. Matsumoto, K. Tani, Organometallics 15
1996) 5246.
OꢁH bond of MeOH.
All the reactions reported in this work presumably
occur through the intermediacy of a platinum–carbene
species derived by initial interaction of the diazo com-
pound with the metal substrate, followed by dinitrogen
loss as demonstrated by fast atom bombardment mass
spectrometric studies [5,7].
[
[
10] R. Bertani, R.A. Michelin, M. Mozzon, A. Sassi, M. Basato, A.
Biffis, G. Martinati, M. Zecca, Inorg. Chem. Commun. 4 (2001)
2
81.
11] (a) R.A. Michelin, G. Facchin, D. Braga, P. Sabatino,
Organometallics 5 (1986) 2265;
(
b) R.A. Michelin, L. Zanotto, D. Braga, P. Sabatino, R.J.
Angelici, Inorg. Chem. 27 (1988) 85;
c) R.A. Michelin, L. Zanotto, D. Braga, P. Sabatino, R.J.
Angelici, Inorg. Chem. 27 (1988) 93;
(
(
(
(
d) R. Bertani, M. Mozzon, R.A. Michelin, Inorg. Chem. 27
1988) 2809;
e) R.A. Michelin, R. Ros, G. Guadalupi, G. Bombieri, F.
Benetollo, G. Chapuis, Inorg. Chem. 28 (1989) 840;
(f) R.A. Michelin, R. Bertani, M. Mozzon, L. Zanotto, F.
Benetollo, G. Bombieri, Organometallics 9 (1990) 1449;
It should be noted that the electrophilicity of the
carbene carbon will most likely be enhanced for the
cationic platinum(II) species as compared with neutral
complexes and this would explain their general higher
reactivity compared to the corresponding neutral com-
plexes in the insertion of carbenes into the OꢁH bond
of alcohols.
(
(
(
g) L. Zanotto, R. Bertani, R.A. Michelin, Inorg. Chem. 29
1990) 3265;
h) R.A. Michelin, R. Bertani, M. Mozzon, G. Bombieri, F.
Benetollo, M.F.C. Guedes da Silva, A.J.L. Pombeiro,
Organometallics 12 (1993) 2372;
(
i) R.A. Michelin, M. Mozzon, B. Vialetto, R. Bertani, F.
Benetollo, G. Bombieri, R.J. Angelici, Organometallics 15 (1996)
096;
j) R.A. Michelin, M. Mozzon, B. Vialetto, R. Bertani, G.
Bandoli, R.J. Angelici, Organometallics 17 (1998) 1220;
k) U. Belluco, R. Bertani, F. Meneghetti, R.A. Michelin, M.
4
(
Acknowledgements
(
Mozzon, J. Organomet. Chem. 583 (1999) 131.
12] R.P. Morgan, J.H. Bejnon, R.H. Bateman, B.N. Green, Int. J.
Mass Spectrom. Ion Phys. 28 (1978) 171.
13] M. Barber, D.J. Bell, M. Eckersley, M. Morris, L.W. Tefler,
Rapid Commun. Mass Spectrom. 2 (1988) 18.
R.A. Michelin thanks MURST Cofin-99 for financial
support.
[
[
[
[
[
14] R.A. Head, Inorg. Synth. 28 (1990) 134.
15] J. Bailar, H. Itatani, Inorg. Chem. 4 (1965) 1618.
16] G. Booth, J. Chatt, J. Chem. Soc. (A) (1966) 634.
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