´
A. Fernandez, J.M. Vila / Journal of Organometallic Chemistry 690 (2005) 3638–3640
3640
ether (40 cm3). Then, a-bromo-p-xylene (8.470 g, 45.78
mmol) in diethyl ether (40 cm3) was added dropwise
and the resulting mixture was refluxed for 1.5 h. To
the cooled reaction bis(dichlorophosphino)methane
(1.458 g, 6.70 mmol) in diethyl ether (40 cm3) was added
dropwise and stirred for 12 h. Ammonium chloride in
water (9 g/100 cm3) was added, stirring continued for
a further 30 min, the mixture extracted with four 50
cm3 portions of ethanol and the combined extracts re-
duced to low volume under vacuum. The residue was
recrystallized from methanol to give a white solid, which
was filtered off and dried in vacuo. Yield: 70%. C33H38P2
(496.61). Anal. Found: C, 79.9; H, 7.6%. Calc.: C, 79.8;
(CH); 125.3 (CH); 124.7 (CH); 39.2 (d, CH2C6H3,
1J(PC) = 28.0 Hz); 32.6 (d, CH2, 1J(PC) = 27.5 Hz);
32.4 (d, CH2, 1J(PC) = 27.1 Hz); 32.0 (d, CH2,
1J(PC) = 28.2 Hz); 25.1 (d, PCH2 P, 1J(PC) = 26.5
Hz); 20.92, 20.85, 20.75, 20.70 (s, 4Me). 31P–{1H}
NMR: d47.22d, d23.01d (2J(PP) = 83.3 Hz).
Acknowledgements
´
We thank the Ministerio de Educacion y Cultura
(BQU2002-04533-C02-01/02) and the Xunta de Galicia
(Proyecto PGIDIT03PXIC1050PN), Spain.
1
H, 7.7. H NMR: d7.1 (m, 16H, C6H4) d3.0 (m, 10H,
PCH2P, PCH2Ph), d2.36 (s, 3H, Me), d2.34 (s, 3H,
Me), d2.33 (s, 3H, Me), d2.31 (s, 3H, Me). 31P–{1H}
NMR: d23.32s.
References
[1] I. Omae, in: Organometallic Intramolecular-coordination Com-
pounds, Elsevier Science, Amsterdam, New York, 1986.
[2] V.V. Dunina, O.A. Zalevskaya, V.M. Potapov, Russ. Chem. Rev.
571 (1984) 250.
3.2. Synthesis of [Mn{(4-MeC6H3CH2)-
(4-MeC6H4CH2)PCH2P(4-MeC6H4CH2)2}(CO)3]
[3] G.R. Newkome, W.E. Puckett, W.K. Gupta, G.E. Kiefer, Chem.
Rev. 86 (1986) 451.
The diphosphine (4-MeC6H4CH2)2PCH2P(4-MeC6-
H4CH2)2 (100 mg, 0.200 mmol) and [MnMe(CO)5] (42
mg, 0.200 mmol) were added to n-octane (50 cm3).
The mixture was heated under reflux (after 15 min a yel-
low color appears) for 7 h. After cooling to room tem-
perature, the solvent was removed under vacuum and
the residue chromatographed in a column packed with
silica gel. Elution with dichloromethane gave a yellow
band from which the final product was obtained as a
yellow solid. Yield: 50%. C36H37O3P2Mn (634.57). Anal.
Found: C, 68.0; H, 5.8%. Calc.: C, 68.1; H, 5.9. IR:
[4] E.C. Constable, Polyhedron 3 (1984) 1037.
[5] M. Pfeffer, Recl. Trav. Chim. Pays-Bas 109 (1990) 56.
[6] M. Albrecht, G. van Koten, Angew. Chem., Int. Ed. 40 (2001)
3750.
[7] J. Dupont, M. Pffefer, J. Spencer, Eur. J. Inorg. Chem. (2001)
1917.
[8] M.I. Bruce, Angew. Chem., Int. Ed. Engl. 86 (1977) 73.
[9] I. Omae, Coord. Chem. Rev. 32 (1980) 235.
[10] (a) A.J. Cheney, B.E. Mann, B.L. Shaw, R.M. Slade, J. Chem.
Soc., Dalton (1971) 3833;
(b) M.A. Bennett, S.K. Bhargava, M. Ke, A.C. Willis, J. Chem.
Soc., Dalton (2000) 3537.
1
m(C@O) 1980s, 1905s, 1880s cmꢀ1. H NMR: d6.91 (s,
[11] R.A. Bennett, M.I. Bruce, F.G.A. Stone, J. Organomet. Chem. 94
(1975) 65.
[12] P.S. Pregosin, R.W. Kuntz, 31P and 13C NMR of transition metal
phosphine complexes, in: P. Diehl, E. Fluck, R. Kosfeld (Eds.),
NMR, vol. 16, Springer, Berlin, 1979.
3
1H, H3), d6.79 (d, 1H, H5, J(H5H6) = 6.8 Hz), d6.35
4
(dd, 1H, H6, J(PH6) = 6.1 Hz), d3.1 (m, 4H, PCH2P,
PCH2Ph), d2.37 (s, 3H, Me), d2.34 (s, 3H, Me), d2.27
(s, 3H, Me), d2.24 (s, 3H, Me).
[13] D.F. Gill, B.L. Shaw, J. Chem. Soc., Chem. Commun. (1972)
65.
2
13C–{1H} NMR: d197.4 (dd, CO, J(PC) = 15.6, 9.5
[14] M.G. Clerici, B.L. Shaw, B. Weeks, J. Chem. Soc., Chem.
Commun. (1973) 516.
2
Hz); d211.3 (t, 2CO, J(PC) = 8.2 Hz); 149.78 (dd, C
Mn, 2J(PC) = 17, 3J(PC) = 5.3 Hz); 139.15 (d, C1,
2J(PC) = 17 Hz); 135.43 (d, C6, 3J(PC) = 4.2 Hz);
134.5–132.7 (m, several CH); 132.4 (CH); 132.2 (d,
[15] M.I. Bruce, B.L. Goodall, F.G.A. Stone, J. Chem. Soc., Dalton
(1978) 687.
[16] A.J. Cheney, B.L. Shaw, J. Chem. Soc., Dalton (1972) 754.
[17] D.D. Perrin, W.L.F. Armarego, Purification of Laboratory
Chemicals, fourth ed., Butterworth-Heinemann, London,
1996.
3
CH, J(PC) = 3.1 Hz); 132.1 (CH); 132.0, 131.9, 131.7,
131.5 (s, 4Cp); 130.2 (s, C3); 129.9 (d, Ci,
2J(PC) = 17.1 Hz); 128.13 (d, Ci, 2J(PC) = 17.0 Hz);
127.85 (d, Ci, 2J(PC) = 17.3 Hz); 126.1 (CH); 125.7
[18] R.B. King, Organometallic Syntheses, Academic Press, New
York, 1965.