J. Albert et al. / Journal of Organometallic Chemistry 595 (2000) 54–58
57
3.7. Cyclometallation of 1 by the system PdCl2, NaCl
and NaOAc·3H2O
3JHH=8.0 Hz (H3). 31P{1H}-NMR (101.2 MHz,
CHCl3, 298 K): 37.23.
A suspension formed by 1.41×10−3 mol (0.397 g) of
1, 1.41×10−3 mol (0.250 g) of PdCl2, 2.42×10−3 mol
(0.141 g) of NaCl, 1.41×10−3 mol (0.191 g) of
NaOAc·3H2O and 20 cm3 of methanol was stirred at
r.t. for 3 days. After that, the suspension was concen-
trated under vacuum and 1.41×10−3 mol (0.370 g) of
PPh3 and 20 cm3 of acetone were added to the residue.
The resulting suspension was stirred at r.t. for 30 min
and then concentrated under vacuum. The residue was
eluted through a column of SiO2 with CHCl3–methanol
(100:2) and the orange band was collected and concen-
trated under vacuum. Addition of diethyl ether (6 cm3)
to the residue produced the precipitation of 4 as a red
powder, which was filtered and dried in vacuum. Yield:
25% (0.238 g).
Acknowledgements
We are grateful to the Direccio´n General de Inves-
tigacio´n Cient´ıfica y Te´cnica (DGICYT) and to the
Generalitat de Catalunya for financial support (Grants
PB96-0164 and SGR-1997-00174).
References
[1] H. Onoue, I. Moritani, J. Organomet. Chem. 43 (1972) 431.
[2] J. Buey, P. Espinet, H.-S. Kitzerov, J. Strauss, Chem. Commun.
(Cambridge) (1999) 441.
[3] M. Ohff, A. Ohff, D. Milstein, Chem. Commun. (1999) 357.
[4] M. Crespo, C. Grande, A. Klein, J. Chem. Soc. Dalton Trans.
(1999) 1629.
3.8. Characterisation data
[5] M. Go´mez, J. Granell, M. Mart´ınez, J. Chem. Soc. Dalton
Trans. (1998) 37.
[6] M. Go´mez, J. Granell, M. Mart´ınez, Organometallics 16 (1997)
2539.
[7] C. Navarro-Ranninger, I. Lo´pez-Solera, A. Alvarez-Valde´s, J.H.
Rodr´ıguez-Ramos, J.R. Masaguer, J.L. Garc´ıa-Ruano,
Organometallics 12 (1993) 4104.
[8] S. Chakladar, P. Paul, K. Venkatsubramanian, K. Nag, J.
Chem. Soc. Dalton Trans. (1991) 2669.
[9] P.W. Clark, S.F. Dyke, C. Smith, C.H.L. Kennard, J.
Organomet. Chem. 330 (1987) 447.
1: Anal. Calc. for C21H15N: C, 89.65; H, 5.38; N,
4.96. Found: C, 89.6; H, 5.4; N, 4.9%. FAB+ (selected
data): 282 ([M+H]+). IR (cm−1): 1622 st (CꢁN).
1H-NMR (500 MHz, CDCl3, 298 K): 9.67 s (CHꢁN),
3
4
8.74 dd, JHH=8.5, JHH=1.0 Hz (H1 and H8), 8.54 s
3
4
(H10), 8.04 dt, JHH=8.0, JHH=1.0 Hz (H4 and H5),
7.55 m (H2 and H7), 7.52–7.48 m (H3, H6 and m-Ph),
7.42 dd, 3JHH=7.5, 4JHH=1.0 Hz (o-Ph), 7.32 tt,
[10] J. Albert, J. Granell, J. Sales, J. Organomet. Chem. 273 (1984)
393.
4
3JHH=6.0, JHH=1.0 Hz (p-Ph).
2: Anal. Calc. for C46H34N2O4Pd2: C, 61.97; H, 3.84;
N, 3.14. Found: C, 61.5; H, 4.1; N, 3.1%. FAB+
(selected data): 445 ([M/2]+), 386 ([M/2−OAc]+), 280
([M/2−OAc−Pd]+). IR (cm−1): 1608 st (CꢁN), 1576
st as (OAc), 1410 st s (OAc). 1H-NMR (500 MHz,
[11] S. Tollari, S. Cenini, C. Tunice, G. Palmisano, Inorg. Chim.
Acta 272 (1998) 18.
[12] J. Albert, J. Granell, A. Luque, M. Font-Bard´ıa, X. Solans, J.
Organomet. Chem. 545–546 (1997) 131.
[13] J. Albert, J. Granell, J. Sales, M. Font-Bard´ıa, X. Solans,
Organometallics 14 (1995) 1393.
[14] J. Albert, M. Go´mez, J. Granell, J. Sales, X. Solans,
Organometallics 9 (1990) 1405.
[15] K. Hiraki, S. Ibaraki, M. Onishi, Y. Ono, J.K. Kawashima, M.
Ando, J. Organomet. Chem. 547 (1997) 199.
[16] H. Yang, M.A. Khan, K.M. Nicholas, J. Chem. Soc. Chem.
Commun. (1992) 210.
[17] J. Albert, J. Barro, J. Granell, J. Organomet. Chem. 408 (1991)
115.
[18] G. De Munno, M. Ghedini, F. Neve, Inorg. Chim. Acta 239
(1995) 155.
[19] J. Albert, R.M. Ceder, M. Go´mez, J. Granell, J. Sales,
Organometallics 11 (1992) 1536.
[20] J. Albert, J. Granell, J. Sales, X. Solans, M. Font-Altaba,
Organometallics 5 (1986) 2567.
[21] L.-Y. Huang, U.R. Aulwurm, F.W. Heinemann, F. Knoch, H.
Kisch, Chem. Eur. J. 4 (1998) 1641.
[22] C.R. Baar, H.A. Jenkins, G.P.A. Yap, R.J. Puddephatt,
Organometallics 17 (1998) 4329.
[23] G. Barea, M.A. Esteruelas, A. Lledo´s, A.M. Lo´pez, E. On˜ate,
J.I. Tolosa, Organometallics 17 (1998) 4065.
[24] G.A. Moehring, C.C. Williams, J. Buford, M. Kaviani, J. Sulko,
P.E. Fanwick, Inorg. Chem. 37 (1998) 3848.
[25] J.M. Vila, M.T. Pereira, J.M. Ortigueira, D. Lata, M. Lo´pez
Torres, J.J. Ferna´ndez, A. Ferna´ndez, H. Adams, J. Organomet.
Chem. 566 (1998) 93.
3
CDCl3, 298 K): 8.12 s (CHꢁN), 8.08 dd, JHH=7.0,
3
4JHH=1.0 Hz (H2), 7.96 s (H10), 7.79 d, JHH=8.0 Hz
3
(H4), 7.55 t, JHH=7.5 Hz (H3), 7.42 m (H5), 7.30 t,
3JHH=8.0 Hz (m-Ph), 7.24–7.20 m (H6, H7 and p-Ph),
7.11 m (H8), 6.94 d, 3JHH=7.5 Hz (o-Ph), 1.38 s
(OAc).
3: Anal. Calc. for C42H28N2Cl2Pd2: C, 59.74; H, 3.34;
N, 3.32. Found: C, 60.2; H, 3.3; N, 3.3%. FAB+
(selected data): 386 ([M/2−Cl]+), 280 ([M/2−Cl−
Pd]+). IR (cm−1): 1608 st (CꢁN).
4: Anal. Calc. for C39H29NClPPd: C, 68.43; H, 4.27;
N, 2.05. Found: C, 68.2; H, 4.4; N, 2.2%. FAB+
(selected data): 648 ([M−Cl]+). IR (cm−1): 1617 st
(CꢁN), 1093 q X-sensitive mode of the coordinated
PPh3. 1H-NMR (500 MHz, CDCl3, 298 K): 9.10 d,
3
4JPH=10 Hz (CHꢁN), 8.54 s (H10), 8.39 d, JHH=8.5
3
3
Hz (H8), 8.06 d, JHH=8.5 Hz (H5), 7.73 d, JHH=8.5
3
3
Hz (o-PhN), 7.70 t, JHH=7.5 Hz (H7), 7.54 t, JHH
=
7.0 Hz (H6), 7.50–7.43 m (m-PhN, o-PhP), 7.37 d,
3
3JHH=8.5 Hz (H4), 7.31 m (p-PhP), 7.29 t, JHH=7.5
Hz (p-PhN), 7.23–7.20 m (m-PhP and H2), 6.42 t,