´
´
´
J. Bravo, J. Castro, S. GarcıaϪFontan, E. M. Lamas, P. RodrıguezϪSeoane
(2 ml), affording a yellowish product that was filtered out. The fil-
trate was kept overnight at Ϫ4 °C affording crystals suitable for X-
Synthesis of fac-[MnBr(CO)3L] (1)
[MnBr(CO)5] (0.2 g, 0.7 mmol) was dissolved in 20 ml of toluene
and 7.3 ml (1.75 mmol) of Ph2POCH2CH2OPPh2 (L) were added
under argon. The reaction mixture was heated at 90 °C for 4 h, the
solvent was removed under vacuum, and the residue was treated
with ethanol, affording a yellow product that was filtered out,
washed with ethanol and dried under vacuum. Yield: 0.42 g (93 %);
mp: 188 °C. C29H24BrMnO5P2 (649.3); C, 53.81 (calc. 53.65); H,
3.79 (3.73) %.
ray structural analysis. Yield: 49 mgl (52 %); mp: 136 °C;
C23H30BrMnO7P2 (615.28); C 45.17 (calc. 44.90); H, 5.13 (4.91) %.
IR (KBr): ν(CO) 2048 w, 1977 s, 1905 m cmϪ1 31P{1H} NMR (CDCl3) δ ϭ
;
184.9 (s); 1H NMR (CDCl3) δ ϭ 7.5Ϫ7.2 (m, 10H, Ph), 4.1Ϫ3.4 (m, 8H,
OCH2CH3), 1.2 (m, 12 H, OCH2CH3).
Synthesis of mer, trans-[MnBr(CO)3{PPh2(OEt)}2]
(5)
MS (8 eV, 150 °C) m/z ϭ 648 (M, <5 %), 564 (M-3CO, 98 %), 571 (M-Ph,
11 %), 569 (M-Br, 35 %). IR (KBr): ν(CO) 2027 s, 1954 m, 1913 s cmϪ1
;
31P{1H} NMR (CDCl3) δ ϭ 153.2 (s); 1H NMR (CDCl3) δ ϭ 4.5 (m, 2H,
CH2), 3.9 (m, 2H, CH2), 7.2Ϫ7.8 (m, 20 H, Ph); 13C{1H} NMR (CDCl3) δϭ
215.8 (m, CO), 219.9 (m, CO), 139.2 (t, J ϭ 22.2 Hz, ipso-C of Ph), 137.6 (t,
J ϭ 8.5 Hz, ipso-C of Ph), 132.3 (t, J ϭ 5.7 Hz, ortho-C), 130.8 (t, J ϭ
6.0 Hz, ortho-C), 128.3 (t, J ϭ 5.1 Hz, meta-C of Ph), 128.2 (t, J ϭ 4.9 Hz,
meta-C of Ph), 131.0 (s, para-C of Ph), 130.7 (s, para-C of Ph), 66.8 (s,
ϪOCH2-CH2OϪ).
Compound 5 was prepared in the same way as compound 4 using
PPh2(OEt) (0.130 ml, 0.6 mmol) as monodentate phosphinite li-
gand. The filtrate was kept overnight at Ϫ4 °C affording yellow
crystals, suitable for X-ray structural analysis. Yield: 45 mgl (43 %)
mp:141 °C; C31H30BrMnO5P2 (679.37); C 55.02 (calc. 54.81); H,
4.63 (4.45) %.
IR (KBr): ν(CO) 2046 w, 1955 s, 1921 m cmϪ1 31P{1H} NMR (CDCl3) δ ϭ
;
Suitable crystals for X-ray structural analyses were obtained from
a solution in 1:20 (v/v) CH2Cl2/EtOH mixture by slow evaporation.
154.1 (s); 1H NMR (CDCl3) δ ϭ 8.0Ϫ7.2 (m, 20H, Ph), 3.7 (m, 4H,
ϪOCH2CH3), 1.2 (t, 6H, JHϪH ϭ 6.9, ϪOCH2CH3). 13C{1H} NMR (CDCl3)
δ ϭ 220.2 (m, CO), 215.7 (m, CO), from 137.6 to 128.0 (C of Ph), 62.9 (m,
OCH2CH3), 16.1 (t, JCϪP ϭ 3.6 Hz, OCH2CH3).
Synthesis of cis,mer-[MnBr(CO)2L{P(OMe)3}] (2)
[MnBr(CO)3L] (100 mg, 0.15 mmol) was dissolved in 20 ml of ben-
zene and 0.078 ml (0.6 mmol) of P(OMe)3 were added under argon.
The reaction mixture was refluxed for 2 h, the solvent removed un-
der vacuum, and the residue treated with a mixture 1:1 (v/v) etha-
nol-methanol, affording a yellowish product that was filtered out,
washed with ethanol and dried under vacuum. Yield: 51.4 mg,
(46 %); mp: 156 °C. C31H33BrMnO7P3 (745.36); C, 50.24 (calc.
49.95); H, 4.75 (4.46) %.
X-ray data collection, structure analysis and
refinement
Crystallographic measurements were obtained on
a Bruker
SMART CCD area-detector diffractometer. All measurements
were performed at room temperature (293 K) using graphite mono-
˚
chromated Mo Kα radiation (λ ϭ 0.71073 A), and were corrected
for Lorentz and polarization effects.The frames were integrated
with the Bruker SMART (control) and Bruker SAINT (integration)
[18] software packages; all data were corrected for absorption using
the program SADABS. The structures were solved by direct meth-
ods using the program SHELXS-97 [19]. All non-hydrogen atoms
were refined with anisotropic thermal parameters by full-matrix
least-squares calculations on F2 using the program SHELXL-97
[20]. Hydrogen atoms were inserted at calculated positions and con-
strained with isotopic thermal parameters. Drawings were pro-
duced with ORTEP [21]. Crystallographic data and structure re-
finement parameters are listed in Table 1. Crystallographic data
(excluding structure factors) have been deposited with the Cam-
bridge Crystallographic Centre as Supplementary Publication No.
CCDC 194893Ϫ194895 for compounds 1, 4 and 5 respectively. Co-
pies of the data can be obtained free of charge on application to The
Director, CCDC, 12 Union Road, Cambridge CB21EZ, UK (FAX:
(ϩ44) 1223 336Ϫ033; E-mail for inquiry: fileserv@ccdc.cam.ac.uk;
e-mail for deposition: deposit@ccdc.cam.ac.uk).
MS (8eV, 150 °C): 744 (M, < 5 %), 564 (MϪ2COϪP(OMe)3, 99 %), 665
(MϪBr, 24 %), 485 (MϪBrϪ2COϪP(OMe)3, 24 %). IR (KBr): ν(CO) 1957 s,
1889 s cmϪ1 31P{1H} NMR (CDCl3) δ ϭ 169.6 (m, P(OMe)3), 153.5 (m,
;
Ph2POCH2CH2OPPh2, PA), 157.5 (m, Ph2POCH2CH2OPPh2, PB); 1H NMR
(CDCl3) δ ϭ 5.0, 4.3, 4.1, 4.0 (4H, 1:1:1:1, each a m, ϪOCH2CH2OϪ ), 3.6
(d, 9H, CH3), 7.2Ϫ8.1 (m, 20 H, Ph); 13C{1H} NMR (CDCl3) δ ϭ 222.3 (m,
CO), 215.8 (m, CO), from 142.5 to 127.2 (C of Ph), 66.4 (d, J ϭ 8.8 Hz,
ϪOCH2-CH2OϪ), 53.4 (d, J ϭ 8.8 Hz, ϪOCH3).
Synthesis of cis,mer-[MnBr(CO)2L{P(OEt)3}] (3)
Compound 3 was prepared in the same way as compound 2 using
P(OEt)3 ( 0.105 ml, 0.6 mmol) as monodentate phosphite ligand.
Yield: 70 mg, (58 %); mp: 159 °C. C34H39BrMn O7P3 (787.44); C,
51.00 (calc. 51.86); H, 5.08 (4.99) %.
MS (8eV, 150 °C ): 786 (M, <5 %), 730 (MϪ2CO, 9 %), 564
(MϪ2COϪP(OMe)3, 99 %), 707 (MϪBr, 11 %), 485 (MϪBrϪ2COϪP-
(OMe)3, 19 %). IR (KBr): ν(CO) 1959 s, 1895 s cmϪ1 31P{1H} NMR
;
(CDCl3) δ ϭ 166.9 (m, P(OEt)3), 153.6 (m, Ph2POCH2CH2OPPh2, PA),
158.2 (m, Ph2POCH2CH2OPPh2, PB); 1H NMR (CDCl3) δ ϭ 7.3Ϫ8.0 (m,
20 H, Ph), 4.9, 4.3, 4.1 [each a m, 4H, 1:1:2 (the last partially masked by
the ethoxy groups), ϪOCH2CH2OϪ], 3.9 (m, 6H, OCH2CH3), 1.1 (m, 9H,
ϪOCH2CH3); 13C{1H} NMR (CDCl3) δ ϭ 222.3 (m, CO), 215.7 (m, CO),
from 142.3 to 126.9 (C of Ph), 66.7 (br s, CH2), 61.6 (d, CH2, J ϭ 8.0 Hz),
15.9 (m, CH3).
Results and Discussion
The reaction of [MnBr(CO)5] with an excess of Ph2POCH2-
CH2OPPh2 (L) during four hours resulted in the complex
[MnBr(CO)3L], identified as fac-[MnBr(CO)3L] by spectro-
scopic and X-ray diffractometric studies (Scheme 1).
Synthesis of mer, trans-[MnBr(CO)3{PPh(OEt)2}2]
(4)
[MnBr(CO)3L] (100 mg, 0.15 mmol) was dissolved in 20 ml of ben-
zene and 0.12 ml (0.6 mmol) of PPh(OEt)2 were added under ar-
gon. The reaction mixture was refluxed for 4 h, the solvent was
removed under vacuum, and the residue was treated with ethanol
Scheme 1 Synthesis of compound 1.
298
Z. Anorg. Allg. Chem. 2003, 629, 297Ϫ302