Synthesis, structure and reactivity of [1,2-Bis(diphenylphosphinite)ethane]bromotricarbonylmanganese(I) with reactions of phosphites, phosphonites. and phosphinites

Article abstract of DOI:10.1002/zaac.200390047

The manganese carbonyl complex [MnBr(CO)₃L] (1), where L = Ph₂POCH₂CH₂OPPh₂, was prepared by reacting [MnBr(CO)₅] with the bidentate ligand 1,2-Bis(diphenylphosphinite)ethane. From this com

Full text of DOI:10.1002/zaac.200390047

Synthesis, Structure and Reactivity of
[1,2-Bis(diphenylphosphinite)ethane]bromotricarbonylmanganese(I)
with Reactions of Phosphites, Phosphonites. and Phosphinites
´
´
´
´
Jorge Bravo, Jesus Castro, Soledad Garcıa-Fontan, Elvira M. Lamas, Pilar Rodrıguez-Seoane*
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Vigo / Spain, Departamento de Quımica Inorganica, Facultade de Ciencias-Quımica, Universidade de Vigo
Received October 21st, 2002.
th
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Dedicated to Professor Alfonso Castineiras on the Occasion of his 60 Birthday.
Abstract. The manganese carbonyl complex [MnBr(CO)3L] (1),
where L ϭ Ph2POCH2CH2OPPh2, was prepared by reacting
[MnBr(CO)5] with the bidentate ligand 1,2-Bis(diphenylphosphini-
te)ethane. From this compound and the appropriate phosphite,
phosphinite or phosphonite ligands were synthesized the complexes
[MnBr(CO)2LLЈ], where LЈ ϭ P(OMe)3 (2) or P(OEt)3 (3) and
[MnBr(CO)3LЈ2], where LЈ ϭPPh(OEt)2 (4) or PPh2(OEt) (5).
The obtained compounds have been characterized by elemental
analysis, mass spectrometry, IR and NMR (1H, 13C and 31P) spec-
troscopies and X-ray diffractometry for the complexes 1, 4 and 5.
Keywords: Manganese; 1,2-Bis(diphenylphosphinite)ethane com-
plexes; Phosphite complexes; Phosphinite complexes; Phosphonite
complexes
Synthese, Struktur und Reaktivität von
[1,2-Bis(diphenylphosphinit)ethan]bromotricarbonylmangan(I) in Reaktionen mit
Phosphiten, Phosphoniten und Phosphiniten
Inhaltsübersicht. Der Mangan-Carbonyl-Komplex [MnBr(CO)3L]
(1) mit L ϭ Ph2POCH2CH2OPPh2 wird durch Umsetzung von
[MnBr(CO)5] mit dem zweizähnigen Liganden 1,2-Bis(diphenyl-
phosphinit)ethan hergestellt. Aus dieser Verbindung werden mit
verschiedenen Phosphit-, Phosphinit- und Phosphonit-Liganden
die Komplexe [MnBr(CO)2LLЈ] mit LЈ ϭ P(OMe)3 (2) und P(OEt)3
(3) sowie [MnBr(CO)3LЈ2] mit LЈ ϭ PPh(OEt)2 (4) und PPh2(OEt)
(5) erhalten. Die Komplexe werden durch Elementaranalysen, Mas-
senspektren, IR- und NMR-Spektren (1H, 13C, 31P) sowie 1, 4 und
5 durch Kristallstrukturanalysen charakterisiert.
Introduction
phinite)ethane]bromotricarbonyl-manganese(I) and its re-
activity with different monodentate phosphite, phosphonite
and phosphinite ligands.
The reactions of [MnX(CO)5] (X ϭ Cl, Br, I) with a variety
of phosphine ligands have been investigated by several
groups of scientists [1Ϫ14]. Substitution of carbonyl groups
and the stereochemistry of the resulting complex is demon-
strated to be dependent, among other factors, on the size
of the ligand.
Relatively little data are available on the bidentate ligand
phosphite complexes. As ligands, phosphites are generally
more electron withdrawing than phosphines and their use
as ancillary ligands may have interesting effects on both the
structure and reactivity of the resulting complexes. The
used ligands have been selected due to their “carbonyl like”
π-acceptor properties together with their low steric require-
ments.
Experimental Section
Materials and instrumentation
All synthetic operations were performed under argon. A standard
vacuum system and Schlenk type glassware were used in handling
metal complexes. Solvents were pre-dried over sodium wire or cal-
cium chloride before reflux and subsequent distillation, under ar-
gon, from a suitable drying agent [15]. Deuterated solvents for
NMR measurements (Aldrich and Merck) were dried over molecu-
lar sieves. 1,2-Bis(diphenylphosphinite)ethane was prepared by the
˜
method of Bolano et al. [16] and [MnBr(CO)5] was obtained from
[Mn2(CO)10] by the method described in the literature [17]. Mono-
dentate phosphites, phosphinites and phosphonites (Aldrich,
Steinheim, Germany) were used as supplied.
We report here on the synthesis and spectroscopic and
diffractometric characterization of [1,2-bis(diphenylphos-
The IR spectra of samples in KBr pellets were recorded on a
Bruker Vector IFS28 FT spectrophotometer, and the NMR spectra
1
on a Bruker AMX 400 spectrometer. H and 13C{1H} are referred
to internal TMS, and 31P{1H} chemical shifts to 85 % H3PO4, with
downfield shifts considered positive. Mass spectra were recorded in
the LSIMS, Csϩ mode on a Micromass Autospec M instrument.
Elemental analyses were carried out on a Fisons EA-1108 appa-
ratus. Melting points were determined on a Gallen Kamp MFB-
595 apparatus and are uncorrected.
´
* Prof. Dra. Pilar Rodrıguez Seoane
Universidade de Vigo.
´
Depart. Quım. Inorg.
EϪ36200 Vigo/Spain
Fax: ϩ34 986 813798
EϪmail: pseoane@uvigo.es
Z. Anorg. Allg. Chem. 2003, 629, 297Ϫ302  2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim 0044Ϫ2313/03/629/297Ϫ302 $ 20.00ϩ.50/0
297

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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

Reactivity of [1,2Bis(diphenylphosphinite)ethane]bromotricarbonylmanganese(I)
Treatment of [1,2-bis(diphenylphosphinite)ethane]bromo-
tricarbonylmanganese(I) [MnBr(CO)3L] with the appropri-
ate monodentate phosphite LЈ ؍ P(OMe)3 or P(OEt)3, in
refluxing benzene for 4 h, resulted in the replacement of
one carbonyl group by LЈ (Scheme 2).
dinated to three terminal carbonyl groups, a Br atom and
a bidentate chelating Ph2POCH2CH2OPPh2 (L) ligand, in
a fac-octahedral arrangement. The MnϪBr bond length,
˚
2.5269(9) A, lies within the range spanned by a MnϪBr sin-
gle bond and is comparable to that previously observed in
˚
fac-[MnBr(CO)3(dmpm)] (2.528(1) A) [11] and fac-[MnBr-
˚
(CO)3(dppe)] (2.517(2) A) [14]. The PϪMnϪP bite of
89.97(5)° is very close to the 90° expected for a regular octa-
hedron and is larger than that found in [MnBr(CO)3(dppe)]
(84.14(10)°) and in [MnBr(CO)3(dmpm)] (71.52(5)°). This
could be due to the number of members in the chelating
ring involved in the bond PϪMnϪP. The MnϪP distances
˚
˚
of 2.3149(14) A and 2.3476(14) A, are also very similar to
those reported in the literature for similar complexes. The
coordination polyhedron around the Mn atom can be ac-
cordingly described as a slightly distorted octahedron, the
main distortions giving as result the following angles:
C(2)ϪMnϪC(3) (85.74(16)°), C(2)ϪMnϪP(1) (175.44(5)°),
C(3)ϪMnϪP(2) (173.73(16)°), C(2)ϪMnϪBr (85.93(3)°)
and C(1)ϪMnϪBr (175.30(15)°).
Scheme 2 Synthesis of compounds 2, 3, 4, and 5.
However, when PPh(OEt)2 or PPh2(OEt) are used as LЈ,
the bidentate ligand, L, is replaced by two monodentate
ligands, LЈ, and complexes [MnBr(CO)3LЈ2] are isolated.
This unexpected effect is probably due to the fact that phos-
phonite and phosphinite ligands are bulkier than phosphite.
Complexes
4 and 5 were identified as mer,trans-
[MnBr(CO)3LЈ2] by spectroscopic and X-ray diffracto-
metric studies.
Structure of mer, trans-[MnBr(CO)3{PPh(OEt)2}2]
(4)
Complex 4 crystallizes in the P21/n space group and con-
sists of discrete units where the manganese atom is located
on a twofold axis perpendicular to the BrϪMnϪC(1)ϪO(1)
axis. A 180° rotation generates two equivalent trans-phos-
phonite ligands and two carbonyl groups, and results in an
orientational disorder where there is a change between Br
and C(1)ϪO(1) groups. This disorder has also been found
in analogous rhenium complexes [22]. The MnϪBr bond
X-Ray structure analysis of complexes 1, 4 and 5.
The structure of complexes 1, 4 and 5 were determined by
X-ray diffractometry. Crystallographic and refinement data
are listed in table 1. Figures 1Ϫ3 show ORTEP plots [21]
with the numbering schemes used and Table 2 lists both
selected bond lengths and angles.
˚
length of 2.487(2) A is within the range of a MnϪBr single
Structure of fac-[MnBr(CO)3L] (1)
bond and slightly smaller than the values found in the com-
˚
¯
The complex 1 crystallizes in the P1 space group and its
pound mer, trans-[MnBr(CO)3{PPh(OMe)2}2] 2.524(7) A
structure consists of discrete units with the Mn atom coor-
[4], and in compound 1, perhaps due to the rotational dis-
Table 1 Crystal data and structure refinement for the obtained structures.
Empirical formula
C29H24BrMnO5P2 (1)
C23H30BrMnO7P2 (4)
C31H30BrMnO5P2 (5)
Formula weight
Temperature
Wavelength
649.27
173(2)K
0.71073 A
307.63
293(2)K
0.71073 A
679.34
293(2)K
0.71073 A
˚
˚
˚
Crystal system
Space group
Unit cell dimensions
triclinic
P1
monoclinic
P21/n
a ϭ 10.1726(18) A.
monoclinic
P21/c
a ϭ 11.6638(7)A.
¯
˚
˚
˚
˚
˚
˚
a ϭ 10.2789(7)A α ϭ 97.3770(10)°.
˚
˚
b ϭ 11.2225(8)A β ϭ 103.6190(10)°.
b ϭ 12.477(2) A β ϭ 95.665(4)°.
b ϭ 14.2608(9)A β ϭ 104.127(2)°.
˚
c ϭ 12.6751(9)A γ ϭ 90.9490(10)°.
c ϭ 10.866(2) A.
c ϭ 18.9589(12)A.
3
3
3
˚
˚
˚
Volume
Z
Calculated density
Absorption coefficient
Crystal size
Theta range for data collection 1.67 to 27.87°
Limiting indices
1407.60(17) A
2
1372.4(4) A
2
3058.2(3) A
4
1.532 Mg/m3
2.039 mmϪ1
0.42 x 0.34 x 0.15 mm
1.489 Mg/m3
2.091 mmϪ1
0.04 x 0.14 x 0.15 mm
2.49 to 28.04°.
1.475 Mg/m3
1.881 mmϪ1
0.2 x 0.13 x 0.09 mm
1.80 to 28.02°.
Ϫ13 Յ h Յ 13, Ϫ10 Յ k Յ 14, Ϫ16 Յ l Յ 15 Ϫ10 Յ h Յ 13, Ϫ16 Յ k Յ 16, Ϫ14 Յ l Յ 9 Ϫ15Յ h Յ 11, Ϫ18 Յ k Յ 18, Ϫ16 Յ l Յ 24
Reflections collected
8683
7427
16267
6730[R(int) ϭ 0.0748]
SADABS
1.0 and 0.797251
0.912
Independent reflections
Absorption correction
Max. and min. transmission
GoodnessϪofϪfit on F2
6071[R(int) ϭ 0.0432]
SADABS
1.00000 and 0.755451
1.075
3049 [R(int) ϭ 0.0631]
SADABS
1.000000 and 0.723467
0.793
Final R indices[I>2 sigma (I)] R1 ϭ 0.0652 , wR2 ϭ 0.1894
R indices (all data) R1 ϭ 0.0784 , wR2 ϭ 0.1972
R1 ϭ 0.0442, wR2 ϭ 0.0721
R1 ϭ 0.1417, wR2 ϭ 0.0895
R1ϭ0.0751 , wR2 ϭ 0.1862
R1ϭ0.2044 , wR2 ϭ 0.2195
Z. Anorg. Allg. Chem. 2003, 629, 297Ϫ302
299

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J. Bravo, J. Castro, S. GarcıaϪFontan, E. M. Lamas, P. RodrıguezϪSeoane
˚
Table 2 Selected bond lengths/A and angles/° for the obtained molecular structures
[MnBr(CO)3(L)] (1)
[MnBr(CO)3(LЈ)] (4)
LЈ؍PPh(OEt)2
[MnBr(CO)3(LЈ)2] (5)
LЈ؍ PPh2(OEt)
MnϪBr
MnϪC(1)
MnϪC(3)
MnϪC(2)
MnϪP(1)
MnϪP(2)
P(1)ϪMnϪBr
P(2)ϪMnϪBr
C(2)ϪMnϪBr
C(1)ϪMnϪBr
C(3)ϪMnϪBr
P(1)ϪMnϪP(2)
C(1)ϪMnϪC(2)
C(2)ϪMnϪC(3)
C(1)ϪMnϪC(3)
C(1)ϪMnϪP(1)
C(2)ϪMnϪP(1)
C(3)ϪMnϪP(1)
C(1)ϪMnϪP(2)
C(2)ϪMnϪP(2)
C(3)ϪMnϪP(2)
2.5269(9)
1.8288(7)
1.830(6)
MnϪBr
MnϪC(1)
MnϪC(3)
MnϪC(2)
MnϪP(1)
MnϪP(1)Ј
P(1)ϪMnϪBr
P(1)ЈϪMnϪBr
C(2)ϪMnϪBr
C(1)ϪMnϪBr
C(2)ЈϪMnϪBr
P(1)ϪMnϪP(1)Ј
C(1)ϪMnϪC(2)
C(2)ϪMnϪC(2)Ј
C(1)ϪMnϪC(2)Ј
C(1)ϪMnϪP(1)
C(2)ЈϪMnϪP(1)
C(2)ЈϪMnϪP(2)
C(1)ϪMnϪP(2)
C(1)ϪMnϪBrЈa)
BrЈϪMnϪBr
2.487(2)
1.774(11)
1.853(5)
1.853(5)
2.267(7)
2.267(7)
90.66(6)
89.33(6)
89.34(13)
176.8(6)
90.66(13)
180.00(5)
88.2(5)
179.999(2)
91.8(5)
87.3(6)
90.32(13)
89.68(13)
92.7(6)
MnϪBr
MnϪC(1)
MnϪC(3)
MnϪC(2)
MnϪP(1)
MnϪP(2)
P(1)ϪMnϪBr
P(2)ϪMnϪBr
C(2)ϪMnϪBr
C(1)ϪMnϪBr
C(3)ϪMnϪBr
P(1)ϪMnϪP(2)
C(1)ϪMnϪC(2)
C(2)ϪMnϪC(3)
C(1)ϪMnϪC(3)
C(1)ϪMnϪP(1)
C(2)ϪMnϪP(1)
C(3)ϪMnϪP(1)
C(1)ϪMnϪP(2)
C(2)ϪMnϪP(2)
C(3)ϪMnϪP(2)
2.5343(15)
1.783(10)
1.8924(11)
1.858(10)
2.304(2)
2.290(2)
93.36(7)
88.16(7)
83.7(3)
173.1(3)
94.85(5)
178.13(10)
90.9(4)
177.9(3)
90.7(3)
90.8(3)
89.0(3)
89.61(7)
87.6(3)
1.847(6)
2.3149(14)
2.3476(14)
89.59(4)
88.41(4)
85.93(3)
175.30(15)
87.80(15)
89.97(5)
90.40(16)
85.74(16)
89.0(2)
94.12(16)
175.44(5)
94.99(16)
94.47(16)
89.01(4)
3.2(6)
180.00(13)
90.1(3)
91.36(7)
173.73(16)
a) Referred to the rotational disorder of bromine and carbonyl atoms.
Symmetry transformations used to generate equivalent atoms: Ј: Ϫx, 2Ϫy, Ϫ2z.
Figure 1 Crystal structure of compound
facϪ[MnBr(CO)3(Ph2POCH2CH2OPPh2)] (1).
Figure 3 Crystal structure of compound mer,transϪ[MnBr(CO)3-
{PPh2(OEt)}2] (5).
order between the Br atom and the CO groups. This kind
of packing disorder is possible in this crystal since a bro-
˚
mine atom with a covalent radius of 1.14 A is similar in size
˚
with a carbonyl group at an interatomic distance of 1.15 A
and will, therefore, coincide with the centre of the carbonyl
CϪO bond.
The symmetry around the manganese atom is slightly dis-
torted from an ideal octahedron, being the C(1)ϪMnϪBr
angle the main expression of this deviation. The MnϪP
˚
bond length of 2.267(7) A is similar to the distances found
in the complex mer,trans-[MnBr(CO)3{PPh(OMe)2}2] [4]
˚
˚
(2.279(8) A and 2.260(8) A), and slightly shorter than the
values observed in complex 1 or in compounds where a bi-
dentate chelating ligand is involved in the MnϪP bond.
Figure 2 Crystal structure of compound mer,transϪ[MnBr(CO)3-
{PPh(OEt)2}2] (4). (Rotational disorder has been eliminated for a
better representation)
300
Z. Anorg. Allg. Chem. 2003, 629, 297Ϫ302

Reactivity of [1,2Bis(diphenylphosphinite)ethane]bromotricarbonylmanganese(I)
This shortening arises probably from both the trans influ-
ence of the CO group and the size of the ligand, producing
less steric hindrance than a bidentate ligand.
manganese atom, which is reflected in the value of the
angles PϪMnϪP (178.13(10)°), C(1)ϪMnϪBr (173.1(3)°),
C(2)ϪMnϪBr (83.7(3)° and C(3)ϪMnϪBr (94.85(5)°). The
˚
˚
MnϪP bond lengths of 2.290(2) A and 2.304(2) A are
slightly longer than those found in complex 4 and slightly
shorter than in complex 1. This could be due to the size of
the monodentate phosphinite ligand, bigger than the ligand
PPh(OEt)2 in complex 4, but not so bulky as the bidentate
ligand in complex 1.
Structure of mer, trans-[MnBr(CO)3{PPh2(OEt)}2]
(5)
Complex 5 crystallizes in the P21/c space group and consists
of discrete units with the manganese atom coordinated to
three (meridional) terminal carbonyl groups, a bromine
atom and two monodentate phosphinite ligands,
PPh2(OEt). The bromine atom is trans to a carbonyl,
whereas the two monodentate phosphinite ligands are trans
to each other.
Spectroscopic results
In the carbonyl-stretching region of the IR spectra, in the
case of complex 1 two strong and one medium ν(CO) bands
at 2027s, 1954m and 1913s cmϪ1 arise. This pattern is
characteristic of a fac-tricarbonyl compound.
There are two bands for complexes 2 and 3 at 1957s ,
1889s and 1958s, 1895s, respectively, in accordance with a
˚
The MnϪBr bond length of 2.5343(15) A is within
the range for a MnϪBr single bond and similar to com-
plex
1
and to the previously observed in
˚
[MnBr(CO)3{PPh(OMe)2}2] [4] (2.524(7) A). There is some
deviation from an ideal octahedral symmetry around the
1
a),b)
Table 3 Selected 31P{1H}, H and 13C-{H1}- NMR data for compounds 1Ϫ5
.
31P{1H} NMR
1H NMR
Compound
δ (PA, PB)
δ PC
δ Ph
δ CH2
δ CH3
[MnBr(CO)3L] (1)
L؍Ph2POEtOPPh2
7.8Ϫ7.2
(m, 20H)
4.5 (m, 2H, L)
3.9 (m, 2H, L)
153.2 (s)
ᎏᎏ
ᎏᎏ
5.0 (m, 1H, L)
4.3 (m, 1H, L)
4.1 (m, 1H, L)
4.0 (m, 1H, L)
[MnBr(CO)2LLЈ] (2)
LЈ؍ P(OMe)3
153.5 (m),
157.5 (m)
8.1Ϫ7.2
(m, 20H)
3.6 (d, 9H, LЈ)
169.6 (m)
166.9 (m)
J(1HϪ31P)ϭ 6.9 Hz
4.9 (m, 1H, L)
4.3 (m, 1H, L)
4.1 (m, 1H, L)
3.9 (m, 7H)
[MnBr(CO)2LLЈ] (3)
LЈ؍ P(OEt)3
153.2 (m),
158.6 (m)
8.0Ϫ7.3
(m, 20H)
1.1 (br s, 9H, LЈ)
(1H L y 6H LЈ)
[MnBr(CO)3LЈ2] (4)
LЈ؍ PPh(OEt)2
7.5Ϫ7.2
(m, 10 H)
184.9(s)
154.1(s)
4.1Ϫ3.4 (m, 8H, LЈ)
3.7 (m, 4H, LЈ)
1.2 (m, 12 H, LЈ)
[MnBr(CO)3LЈ2] (5)
LЈ؍ PPh2(OEt)
8.0Ϫ7.2
(m, 20 H)
1.2 (t, 6H, LЈ)
J(1HϪ31P)ϭ 6.9 Hz
13C{1H}؊NMR
Compound
δ CO
δ CH2
δ CH3
[MnBr(CO)3(L)] (1)
L؍Ph2POEtOPPh2
219.9 (m)
215.8 (m)
66.8 (s) (L)
ᎏᎏ
[MnBr(CO)2(L)LЈ] (2)
LЈ؍ P(OMe)3
222.3 (m)
215.8 (m)
66.4 (br s) (L)
53.4(d), LЈ
J(13CϪ31P)ϭ 8.8 Hz
J(13CϪ31P)ϭ 8.8 Hz
66.7 (br s) (L)
61.6 (d), LЈ
[MnBr(CO)2(L)LЈ] (3)
LЈ؍ P(OEt)3
222.3 (m)
215.7 (m)
15.9 (d), LЈ
J(13CϪ31P)ϭ 3 Hz
J(13CϪ31P)ϭ 8.0 Hz
[MnBr(CO)3(LЈ)2] (4)
LЈ؍ PPh(OEt)2
220.2 (m)
215.2 (m)
62.7 (br s), LЈ
62.9 (m), LЈ
16.1 (br s); LЈ
[MnBr(CO)3(LЈ)2] (5)
LЈ؍ PPh2(OEt)
220.2 (m)
215.7 (m);
16.1 (t);LЈ
J(13CϪ31P)ϭ3.6 Hz
a) In CDCl3, δϭ ppm, sϭ singlet, br sϭ broad singlet, mϭ multiplet, dϭ doublet, tϭ triplet
b) See scheme 3.
Z. Anorg. Allg. Chem. 2003, 629, 297Ϫ302
301

´
´
´
J. Bravo, J. Castro, S. GarcıaϪFontan, E. M. Lamas, P. RodrıguezϪSeoane
cis,mer-[MnBr(CO)3LLЈ] symmetry, as the cases of similar
cis,mer-[ReBr(CO)3LLЈ] [24].
indicating the different nature of PA, PB and PC nuclei (see
Scheme 3 and Table 3).
The complexes [MnBr(CO)3LЈ2] show the three ν(CO)
bands analogous to the synthesized complex of Mn with
similar monodentate ligands [25].
´
Acknowledgements. We would like to thank Dr. Ezequiel. M. Vaz-
´
quez-Lopez, University of Vigo (Spain) for the resolution of the
structure for complex 4.
1
The H NMR spectrum of compound 1 is very similar
We thank the CACTI NMR and X-ray services of the University
of Vigo for recording the NMR spectra and collecting X-ray data.
to that of the parent compound [ReBr(CO)3L] showing the
signal corresponding to the Ϫ(CH2)2Ϫ group as a two sets
of multiplets at 3.9 and 4.5 ppm [16].
References
The 13C{1H} NMR spectrum shows two multiplets at
215.8 and 219.9 ppm, being the latter significantly wider.
According to these data, the former could be assigned to
the CO in cis-position with the P nuclei of the bidentate
ligand, and the latter to the CO in trans to the bidentate
ligand. (J(CϪPtrans) are higher than the J(CϪPcis.).
The signal of 31P{1H} NMR spectrum is a singlet that
shows the magnetic equivalence of both P atoms of the bi-
dentate ligand.
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´
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E. M. Vazquez-Lopez, Polyhedron 1999, 18, 1431.
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[22] R. Carballo, A. Castin˜eiras, S. Garcıa-Fontan, P. Losada-
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Gonzalez, U. Abram, E. M. Vazquez-Lopez, Polyhedron 2001,
Scheme 3 Schematic representation of compounds 2 and 3.
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For compound 2, 13C{1H}NMR spectrum shows two
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´
´
´
[24] F. Fernandez-Garcıa, S. Bolan˜o, R. Carballo, S. Garcıa-
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Fontan, J. Bravo, Polyhedron 2001, 20, 2675.
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302
Z. Anorg. Allg. Chem. 2003, 629, 297Ϫ302