Tricarbonyl derivatives of manganese(I) with diphosphinite chelating ligands

Article abstract of DOI:10.1002/zaac.200570016

Reaction of [MnBr(CO)₃L] [L = Ph₂POCH ₂CH₂OPPh₂, L¹, {(CH ₃)₂CH}₂POCH₂CH ₂OP{CH(CH₃)₂}₂, L²

Full text of DOI:10.1002/zaac.200570016

Tricarbonyl Derivatives of Manganese(I) with Diphosphinite Chelating Ligands
´
´
´
Jorge Bravo, Jesus A. Castro, Eduardo Freijanes*, Soledad Garcıa؊Fontan, Elvira M. Lamas, and
´
Pilar Rodrıguez-Seoane*
´
´
´
Vigo/Spain, Departamento de Quımica Inorganica, Facultade de Quımica, Universidade de Vigo
Received November 26th, 2004; accepted March 10th, 2005.
Abstract. Reaction of [MnBr(CO)3L] [L ϭ Ph2POCH2CH2OPPh2,
L1, L2]
{(CH3)2CH}2POCH2CH2OP{CH(CH3)2}2, with
spectroscopies. In the case of [Mn(O3SCF3)(CO)3L1],
[Mn(O2CCF3)(CO)3L1], [MnCl(CO)3L1], [Mn(CH3CN)(CO)3L2]-
(O3SCF3), [Mn(CN)(CO)3L2] and [Mn(O2CCF3)(CO)3L2], together
with the previously synthesized complex [MnBr(CO)3L2], suitable
crystals for X-ray structural analysis were isolated. In all of them
the Mn atom adopts six-coordination by bonding to the three CO
ligands, the two P atoms of L and either one C atom (CN), one
oxygen atom (O2CCF3, O3SCF3), one N atom (CH3CN, SCN) or
the halogen atom (Cl, Br).
AgO3SCF3 and AgO2CCF3 in dichloromethane afforded the new
complexes [Mn(O3SCF3)(CO)3L] and [Mn(O2CCF3)(CO)3L],
respectively. Substitution of O3SCF3 resulted in the new species
[Mn(SCN)(CO)3L], [Mn(NCCH3)(CO)3L](O3SCF3) and, in the
case of L2, [Mn(CN)(CO)3L2]. By contrast, any attempt to displace
the O2CCF3 ligand in the same way was unsuccessful. After main-
taining for some days the complex [Mn(CH3CN)(CO)3L1](O3SCF3)
in dichloromethane at room temperature, the new complex
[MnCl(CO)3L1] was formed. All the new complexes were characte-
rized by elemental analysis, mass spectrometry and IR and NMR
Keywords: Manganese; Diphosphinite complexes; Chelating ligands
1 Introduction
This paper describes the isolation and characterization of
the new complexes arisen from this substitution, as well as
the unexpected chloro-complex [MnCl(CO)3L1], formed
after maintaining for some days one of the aforesaid com-
pounds, [Mn(CH3CN)(CO)3L1](O3SCF3), in dichlorometh-
ane.
The synthesis of transition metal complexes containing a
weakly bound ligand has been widely treated, since such
compounds are useful as a source of other species resulting
from the substitution of the labile ligand for another more
coordinating base [1]. Furthermore, this kind of complexes
is of great interest for catalytic purposes: in fact, a require-
ment for catalysis is the availability of free coordination
sites on the metal atom. In this sense, the triflate (O3SCF3)
anion is usually considered a special case, since its lability
is strongly dependent on the electronic nature of the metal
atom [2Ϫ4]. So that, in an electron-donating ligand en-
vironment, such as [Ti(Cp)2(O3SCF3)2], both triflate ligands
are much more easy to substitute than in, for example, [Re(-
O3SCF3)(CO)5], where they can only be replaced by strong
donors [5, 6].
In a previous work [7], we reported the synthesis of a
series of complexes resulting from the substitution of two
CO ligands from [MnBr(CO)5] for a variety of phosphite,
phosphonite and phosphinite bidentate ligands. By using
two of those complexes as starting material, we carried out
the abstraction of Br and its substitution for triflate and
trifluoroacetate ligands. Subsequently, the new complexes
provided the possibility of substituting the loosely held
O3SCF3 ligand by other more basic ligands.
2 Experimental Section
2.1 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 [8]. Deuterated solvent (CDCl3
Merck) for NMR measurements was dried over molecular sieves.
1,2-Bis(diphenylphosphinoxy)ethane and 1,2 bis(diisopropylphos-
phinoxy)ethane were prepared as described previously [9],
[MnBr(CO)5] was obtained from [Mn2(CO)10] by the method de-
scribed in literature [10] and the starting product [MnBr(CO)3L1]
has been previously reported [7]. AgSO3CF3, AgCO2CF3 (Aldrich),
CH3CN, KCN and KSCN (Merck) were used as supplied.
The IR spectra of samples in KBr pellets were recorded on a
Bruker Vector 22 FT spectrophotometer, and NMR spectra on a
Bruker AMX 400 spectrometer. 1H and 13C{1H} signals are re-
ferred to internal TMS, 31P{1H} chemical shifts to 85 % H3PO4,
and 19F{1H} signals to CFCl3 with downfield shifts considered
positive. Mass spectra were recorded in the LSIMS, Csϩ mode on
a Micromass Autospec M instrument. Elemental analyses were car-
ried out on a Fisons EAϪ1108 apparatus. Melting points were de-
termined on a Gallenkamp MFBϪ595 apparatus and are uncor-
rected.
* Eduardo Freijanes
´
Pilar Rodrıguez-Seoane
´
Facultade de Quımica
Universidade de Vigo
E-36200 Vigo/Spain
Fax: ϩ34-986-813798
E-mail (E.F.): erivas@uvigo.es
Z. Anorg. Allg. Chem. 2005, 631, 2067Ϫ2074
DOI: 10.1002/zaac.200570016
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
2067

´
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J. Bravo, J. A. Castro, E. Freijanes, S. GarcıaϪFontan, E. M. Lamas, P. Rodrıguez-Seoane
lowish crystals of the chlorine derivative, suitable for XϪray struc-
tural analysis, were separated. C29H24ClMnO5P2 (604): C, 56.9
(calc. 57.6); H, 3.9 (4.0) %.
2.2 Synthesis of the complexes
[Mn(O3SCF3)(CO)3L1] (1)
[MnBr(CO)3L1] (0.10 g, 0.15 mmol) and AgSO3CF3 (0.04 g,
0.15 mmol) were dissolved in CH2Cl2 (15 cm3). The reaction mix-
ture was refluxed for 2 h and filtered through celite. The solvent
was removed under vacuum from the obtained solution, and the
residue was triturated with ethanol, affording a yellow product that
was filtered out, washed with ethanol and vacuum dried. Yield:
0.08 g (74 %); mp: 175 °C. C30H24F3MnO8P2S (718.46): C, 49.9
(calc. 50.1); H, 3. 7 (3.4); S, 4.3 (4.5) %.
MS (8 eV, 150 °C) m/z ϭ 604 (M, <5 %), 520 (MϪ3CO, 100 %), 569 (MϪCl,
< 5 %), 485 (MϪCOϪCl, 28 %). IR (KBr): ν(CO) 2034, 1978, 1908 cmϪ1
;
31P{1H} NMR (CDCl3) δ ϭ 153.4 (s); 1H NMR (CDCl3) δ ϭ 4.54 (m, 2H,
CH2), 3.98 (m, 2H, CH2), 7.89-7.24 (m, 20 H, Ph).
[Mn(O2CCF3)(CO)3L1] (5)
[MnBr(CO)3L1] (0.10 g, 0.15 mmol) and AgCO2CF3 (0.03 g,
0.15 mmol) were dissolved in 20 cm3 of CH2Cl2. The reaction mix-
ture was refluxed for 3 h and filtered through celite. From the ob-
tained solution solvent was removed under vacuum, and the residue
was triturated with ethanol, affording a yellow product that was
filtered off, washed with ethanol and vacuum dried. Yield: 0.07 g
(71 %); mp: 165 °C. C31H24F3MnO7P2 (682.41): C, 54.0 (calc. 54.5);
H, 3.8 (3.6) %.
MS (8 eV, 150 °C) m/z ϭ 718 (M, <5 %), 634 (MϪ3CO, 25 %), 485
(MϪ3COϪSO3CF3,
100 %),
569
(MϪSO3CF3,
88 %),
541
(MϪSO3CF3ϪCO, <5 %). IR (KBr): ν(CO) 2041, 1968, 1929 cmϪ1
;
31P{1H}
NMR (CDCl3) δ ϭ 157.5 (s); 19F{1H} NMR (CDCl3) δϭ Ϫ77.3 (s) ; 1H
NMR (CDCl3) δ ϭ 4.07 (m, 4H, CH2), 7.5-7.7 (m, 20 H, Ph); 13C{1H} NMR
(CDCl3,
δ ppm): 213.0 (m, CO), 137.5-127.9 (m, Ph), 66.6 (s,
ϪOCH2ϪCH2OϪ), 118.6 (q, JC-F ϭ 319 Hz, O3SCF3).
Suitable crystals for XϪray structural analysis were obtained from
a solution of EtOH by slow evaporation.
MS (8 eV, 150 °C) m/z ϭ 682 (M, <5 %), 598 (MϪ3CO, 100 %), 485
(MϪ3COϪOOCCF3,
100 %),
569
(MϪOOCCF3,
39 %),
541
;
(MϪOOCCF3ϪCO, <5 %). IR (KBr): ν(CO) 2033, 1969, 1933, 1913 cmϪ1
31P{1H} NMR (CDCl3) δ ϭ 158.6 (s); 19F{1H} NMR (CDCl3) δ ϭ Ϫ74.7
(s); 1H NMR (CDCl3) δ ϭ 4.32 (m, 2H, CH2), 4.14 (m, 2H, CH2), 7.58-7.45
(m, 20 H, Ph); 13C{1H} NMR (CDCl3, δ): 213.9 (m, CO), 161.9 (m,
O2CCF3), 161.5 (m, O2CCF3), 137.5-127.4 (m, Ph), 66.3 (s,
ϪOCH2ϪCH2OϪ), 114.4 (q, JC-F ϭ 291 Hz, O2CCF3).
[Mn(SCN)(CO)3L1] (2)
From [Mn(O3SCF3)(CO)3L1] (0.08 g, 0.13 mmol) and an excess of
KSCN (0.05 g, 0.60 mmol), a solution in a dichloromethane/meth-
anol mixture (10/5 cm3) was formed and stirred for 24 h at room
temperature. The solvent was then removed under vacuum and di-
chloromethane was added to the residue in order to eliminate the
excess of KSCN, which was filtered off. The solvent of the resulting
solution was removed under vacuum and the obtained product was
triturated with diethyl ether affording a yellowish product, which
was washed with diethyl ether and vacuum dried. Yield: 0.02 g
(38 %); mp: 157 °C. C30H24NMnO5P2S (627.47): C, 57.8 (calc.
58.1); H, 4.0 (4.0); N, 2.3 (2.3); S, 5.3 (5.3) %.
Suitable crystals for XϪray structural analysis were obtained from
an ethanol solution by slow evaporation.
[MnBr(CO)3L2] (6)
[MnBr(CO)5] (0.20 g, 0.73 mmol) was dissolved in 15 cm3 of tolu-
ene and 9 ml (2 mmol) of {(CH3)2CH}2POCH2CH2OP{CH-
(CH3)2}2 (L2) were added under argon. The reaction mixture was
heated at 90 °C for 3 h, the solvent was removed under vacuum,
and the resulting oil was triturated with ethanol, yielding a yellow
product that was filtered out, washed with ethanol and dried under
vacuum. Yield: 0.37 g (70 %); mp: 149 °C. C17H32BrMnO5P2
(513.23): C, 39.9 (calc. 39.8); H, 6.4 (6.3) %.
MS (8 eV, 150 °C) m/z ϭ 627 (M, 14 %), 569 (MϪSCN, <5 %), 543
(MϪ3CO, 56 %), 485 (MϪ3COϪSCN, 34 %). IR (KBr): ν(CO) 2035, 1970,
1933; ν(CN) 2099; ν(CS) 818 cmϪ1 31P{1H} NMR (CDCl3) δ ϭ 156.2 (s);
;
1H NMR (CDCl3) δ ϭ 4.29 (m, 2H, CH2), 3.97 (m, 2H, CH2), 7.92-7.26 (m,
20 H, Ph); 13C{1H} NMR (CDCl3, δ): 213.3 (m, CO), 144.9-127.4 (m, Ph),
65.5 (s, ϪOCH2ϪCH2OϪ), 124.0 (s, SCN).
MS (8 eV, 150 °C) m/z ϭ 512 (M, <5 %), 428 (MϪ3CO, 100 %), 433 (MϪBr,
74 %), 377 (MϪBrϪ2CO, 19 %), 349 (MϪBrϪ3CO, 32 %). IR (KBr): ν(CO)
2016, 1949, 1903 cmϪ1 31P{1H} NMR (CDCl3) δ ϭ 180.0 (s); 1H NMR
;
[Mn(CH3CN)(CO)3L1](O3SCF3) (3)
(CDCl3) δ ϭ 4.39 (m, 2H, CH2), 3.84 (m, 2H, CH2), 2.95 (m, 2H, CH), 2.57
(m, 2H, CH), 1.28 (m, 24 H, CH3); 13C{1H} NMR (CDCl3, δ): 215.4 (m,
CO), 64.9 (s, ϪOCH2ϪCH2OϪ), 30.9 (vt, 1JC-P ϩ 3JC-P ϭ 13, CHCH3), 30.5
(m, CHCH3), 17.5 (s, CHCH3), 16.8 (s, CHCH3), 16.5 (s, CHCH3), 16.2
(s, CHCH3).
[Mn(O3SCF3)(CO)3L1] (0.08 g, 0.13 mmol) was disolved in CH2Cl2
(15 cm3) and an excess of CH3CN (0.65 mmol) was added. After
stirring for 1 h at room temperature, the solvent was removed under
vacuum and the residue was triturated with n-hexane, affording a
brown product that was filtered out, washed with n-hexane and
dried under vacuum. Yield: 0.08 g (89 %); mp: 148 °C.
C32H27F3NMnO8P2S (759.46): C, 49.9 (calc. 50.6); H, 3.8 (3.6); N,
1.6 (1.8); S, 4.0 (4.2) %.
Suitable crystals for XϪray structural analysis were obtained by
slow evaporation from an ethanol solution.
[Mn(O3SCF3)(CO)3L2] (7)
MS (8 eV, 150 °C) m/z
ϭ
610 (MϪSO3CF3, 18 %), 569
(MϪCH3CNϪSO3CF3, 95 %), 485 (MϪCH3CNϪ3COϪSO3CF3, 100 %).
[MnBr(CO)3L2] (0.10 g, 0.20 mmol) and AgSO3CF3 (0.05 g,
0.20 mmol) were dissolved in 20 cm3 of CH2Cl2. The reaction mix-
ture was refluxed for 3 h and filtered through celite. Solvent was
then removed from the solution under vacuum and ethanol was
added to the residue, affording a yellowish product that was filtered
out, washed with n-hexane and dried under vacuum. Yield: 0.12 g
(65 %); mp: 125 °C. C18H32F3MnO8P2S (582.39): C, 37.0 (calc.
37.1); H, 5.8 (5.5); S, 5.3 (5.5) %.
IR (KBr): ν(CO) 2047, 1984, 1946 cmϪ1; ν(CN) 2360 cmϪ1
;
31P{1H} NMR
(CDCl3)) δ ϭ 160.0 (s); 19F{1H} NMR (CDCl3) δ ϭ Ϫ79.0; 1H NMR
(CDCl3) δ ϭ 2.01 (m, 3H, CH3), 4.29 (m, 2H, CH2), 4.12 (m, 2H, CH2),
7.69-7.27 (m, 20 H, Ph); 13C{1H} NMR (CDCl3, δ): 213.2 (m, CO), 137.8-
128.2 (m, Ph), 66.9 (s, ϪOCH2ϪCH2OϪ), 128-135 (m, O3SCF3, masked by
Ph), 3.8 (s, CH3CN), 125.2 (s, CH3CN).
[MnCl(CO)3L1] (4)
After maintaining the compound [Mn(CH3CN)(CO)3L1](SO3CF3)
for 2 days at room temperature in dichloromethane solution, yel-
MS (8 eV, 150 °C) m/z ϭ 582 (M, <5 %), 498 (MϪ3CO, 25 %), 377
(MϪ2COϪSO3CF3,
32 %),
433
(MϪSO3CF3,
100 %),
349
(MϪSO3CF3Ϫ3CO, 62 %). IR (KBr): ν(CO) 2028, 1956, 1922 cmϪ1
;
31P{1H}
2068
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2005, 631, 2067Ϫ2074

Tricarbonyl Derivatives of Manganese(I) with Diphosphinite Chelating Ligands
NMR (CDCl3) δ ϭ 183.0 (s); 19F{1H} NMR (CDCl3) δ ϭ Ϫ77.5 (s); 1H
NMR (CDCl3) δ ϭ 4.04 (m, 4H, CH2), 2.61 (m, 4H, CH), 1.32 (m, 24 H,
(KBr): ν(CO) 2014, 1946, 1921; ν(CN) 2112 cmϪ1 31P{1H} NMR (CDCl3)
;
δ ϭ 186.2 (s); 1H NMR (CDCl3) δ ϭ 4.45 (m, 2H, CH2), 3.89 (m, 2H, CH2),
2.75 (m, 2H, CH), 2.52 (m, 2H, CH), 1.27 (m, 24 H, CH3).
CH3); 13C{1H} NMR (CDCl3, δ): 222.9 (m, CO), 214.6 (m, CO), 119.6 (q,
1
JC-F ϭ 318, O3SCF3 ), 66.9 (s, ϪOCH2ϪCH2OϪ), 33.2 (vt, JC-P
ϩ ϭ
3JC-P
1
ϩ
3JC-P ϭ 6 Hz, CH), 18.3 (m, CH3).
Suitable crystals for XϪray structural analysis were obtained by
13 Hz, CH-CH3), 31.0 (vt, JC-P
slow evaporation from an ethanol solution.
[Mn(SCN)(CO)3L2] (8)
[Mn(O2CCF3)(CO)3L2] (11)
[Mn(O3SCF3)(CO)3L2] (0.08 g, 0.12 mmol) and an excess of KSCN
(0.06 g, 0.60 mmol) were dissolved in a dicloromethane/methanol
mixture (10/5 cm3). This solution was stirred for 24 h at room tem-
perature. The solvent was then removed under vacuum and di-
chloromethane was added to the residue in order to eliminate the
excess of KSCN, which was filtered off. The solvent of the resulting
solution was also removed under vacuum and the obtained product
was triturated with n-hexane affording a yellowish product, which
was washed with the same solvent and vacuum dried. Yield: 0.03 g
(46 %); mp: 110 °C. C18H32MnNO5P2S (491.40): C, 43.7 (calc.
43.9); H, 6.9 (6.5); N, 2.9 (2.8); S, 6.3 (6.5) %.
[MnBr(CO)3L2] (0.08 g, 0.17 mmol) and AgCO2CF3 (0.04 g,
0.17 mmol) were dissolved in 20 cm3 of CH2Cl2. The reaction mix-
ture was refluxed for 4 h and filtered through celite. From the ob-
tained solution the solvent was removed under vacuum, and the
residue was triturated with ethanol, affording a yellowish product
that was filtered out, washed with hexane and dried under vacuum.
Yield: 0.05 g (53 %); mp: 129 °C. C19H32F3MnO7P2 (546.34): C,
41.2 (calc. 41.7); H, 6.1 (5.9) %.
MS (8 eV, 150 °C) m/z ϭ 546 (M, <5 %), 462 (MϪ3CO, 100 %), 377
(MϪ2COϪOOCCF3,
27 %),
433
(MϪOOCCF3,
89 %),
349
;
(MϪOOCCF3Ϫ3CO, 48 %). IR (KBr): ν(CO) 2024, 1954, 1906 cmϪ1
MS (8 eV, 150 °C) m/z ϭ 491 (M, <5 %), 407 (MϪ3CO, 13 %), 435
(MϪ2CO, 13 %), 433 (MϪSCN, 16 %), 349 (MϪSCNϪ3CO, 12 %). IR
31P{1H} NMR (CDCl3) δ ϭ 183.4 (s); 19F{1H} NMR (CDCl3) δϭ Ϫ75.1
(s); 1H NMR (CDCl3) δ ϭ 4.28 (m, 2H, CH2), 3.95 (m, 2H, CH2), 2.58 (m,
2H, CH), 2.44 (m, 2H, CH), 1.23 (m, 24 H, CH3); 13C{1H} NMR (CDCl3,
(KBr): ν(CO) 2024, 1956, 1918; ν(CN) 2103 cmϪ1 31P{1H} NMR (CDCl3)
;
δ ϭ 183.4 (s); 1H NMR (CDCl3) δ ϭ 4.13 (m, 2H, CH2), 3.94 (m, 2H, CH2),
2.54 (m, 4H, CH), 1.27 (m, 24 H, CH3); 13C{1H} NMR (CDCl3, δ): 214.7
(m, CO), 207.7 (m, CO), 144.6 (m, SCN), 66.1 (s, ϪOCH2ϪCH2OϪ), 31.9
δ): 221.0 (m, CO), 215.5 (m, CO), 162.5 (m, O2CCF3 ), 115.4 (q, JC-F
ϭ
ϭ
1
291 Hz, O2CCF3), 66.4 (s, ϪOCH2ϪCH2OϪ), 31.8 (vt, JC-P
ϩ
3JC-P
1
13 Hz, CHCH3), 30.2 (vt , JC-P
ϩ
3JC-P ϭ 5 Hz, CHCH3), 17.2 (m, CH3).
1
1
(vt, JC-P
ϩ ϩ
3JC-P ϭ 13 Hz, CHCH3), 31.5 (vt, JC-P 3JC-P ϭ 5 Hz,
CHCH3), 17.7 (s, CH3), 17.3 (s, CH3), 17.2 (s, CH3), 17.1 (s, CH3).
2.3 X؊ray data collection, structure analysis and
refinement
[Mn(CH3CN)(CO)3L2](SO3CF3) (9)
To 0.07 g (0.01 mmol) of [Mn(O3SCF3)(CO)3L2] dissolved in
15 cm3 of CH2Cl2 an excess of CH3CN (0.05 mmol) was added.
After stirring the mixture for 1 h at room temperature, the solvent
was removed under vacuum and the residue was triturated with
hexane, affording a brown product that was filtered out, washed
with hexane and dried under vacuum. Yield: 0.04 g (52 %); mp:
137 °C. C20H35F3MnNO8P2S (623.44): C, 38.0 (calc. 38.5); H, 5.9
(5.7); N, 2.0 (2.2); S, 4.9 (5.1) %.
Crystallographic measurements were obtained on
SMART CCD areaϪdetector diffractometer. All of them were per-
a Bruker
formed at room temperature (293 K) using graphite monochrom-
˚
ated Mo Kα radiation (λ ϭ 0.71073 A). All data were corrected
for absorption using the program SADABS [11]. The structures
were solved by direct methods using the program SHELXSϪ97
[12]. All non-hydrogen atoms were refined with anisotropic thermal
parameters by fullϪmatrix leastϪsquares calculations on F2 using
the program SHELXLϪ97 [12]. Hydrogen atoms were inserted at
calculated positions and constrained with isotopic thermal param-
eters. Drawings were produced with ORTEP [13]. Crystallographic
data and structure refinement parameters are listed in tables 1 and
2. Crystallographic data (excluding structure factors) have been de-
posited with the Cambridge Crystallographic Centre as Sup-
plementary Publication No. CCDC 256209-256215 for compounds
1, 5, 4, 6, 9, 10 and 11, respectively. Copies of the data can be
obtained free of charge on application to The Director, CCDC, 12
Union Road, Cambridge CB21EZ, UK (FAX: (ϩ44) (1223) 3
36Ϫ0 33; EϪmail for inquiry: fileserv@ccdc.cam.ac.uk.
MS (8 eV, 150 °C) m/z
ϭ
474 (MϪSO3CF3, 28 %), 433
(MϪSO3CF3ϪCH3CN, 100 %), 377 (MϪSO3CF3ϪCH3CNϪ2CO, 16 %),
349 (MϪSO3CF3ϪCH3CNϪ3CO, 22 %). IR (KBr): ν(CO) 2035, 1969,
1937 cmϪ1 31P{1H} NMR (CDCl3) δ ϭ 178.0 (s); 19F{1H} NMR (CDCl3)
;
δ ϭ Ϫ79.4(s); 1H NMR (CDCl3) δ ϭ 4.2 (m, 4H, CH2), 2.68 (m, 4H, CH),
1.28 (m, 24 H, CH3); 13C{1H} NMR (CDCl3, δ): 218.9 (m, CO), 214.6 (m,
1
CO), 134.7 (s, CH3CN), 67.6 (s, ϪOCH2ϪCH2OϪ), 33.0 (vt, JC-P
ϩ
3JC-
1
ϭ 13 Hz, CH), 32.2 (vt, JC-P
ϩ
3JC-P ϭ 6 Hz, CH), 17.8 (m, CH3), 5.3
P
(s, CH3CN).
Suitable crystals for XϪray structural analysis were obtained by
slow evaporation from an ethanol solution.
[Mn(CN)(CO)3L2] (10)
[Mn(O3SCF3)(CO)3L2] (0.07 g, 0.12 mmol) and an excess of KCN
(0.04 g, 0.60 mmol) were dissolved in a dichloromethane/methanol
mixture (10/5 cm3). After stirring for 24 h at room temperature, the
solvent was removed under vacuum and the residue was dissolved
in dicloromethane, affording a brown solid (the excess of KCN)
which was filtered off. From the solution the solvent was removed
under vacuum and the resulting oil was triturated with n-hexane,
affording a yellowish product which was washed with the same sol-
vent and dried under vacuum. Yield: 0.02 g (45 %); mp: 115 °C.
C18H32MnNO5P2 (459.34): C, 45.5 (calc. 47.1); H, 7.0 (7.0); N,
3.3 (3.1) %.
3 Results and Discussion
3.1 Synthesis of the complexes
Substitution of the bromo ligand, in the starting complexes,
by triflate or trifluoroacetate ligands, was carried out in
each case by direct reaction with the adequate silver salt
and subsequent isolation of the new complex from the re-
sulting solution. Nevertheless, the easiness of ulterior dis-
placement of the new ligand by another more coordinating
base showed not to be the same in all cases. Schemes 1 and
2 summarize this different behaviour: while any attempt to
displace the trifluoroacetate ligand was unsuccessful, trifl-
MS (8 eV, 150 °C) m/z ϭ 460 (Mϩ, 33 %), 375 (MϪ3CO, 100 %), 377
(MϪ2COϪCN, 8 %), 431 (MϪCO, 7 %), 349 (MϪCNϪ3CO, 26 %). IR
Z. Anorg. Allg. Chem. 2005, 631, 2067Ϫ2074
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© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
2069

´
´
´
J. Bravo, J. A. Castro, E. Freijanes, S. GarcıaϪFontan, E. M. Lamas, P. Rodrıguez-Seoane
Table 1 Crystal data and structure refinement details for complexes 1, 4 and 5.
1
4
5
Empirical formula
Formula weight
Temperature /K
C30H24F3MnO8P2S
718.43
293(2)
C29H24ClMnO5P2
604.81
293(2)
C31H24F3MnO7P2
682.38
293(2)
˚
Wavelength /A
0.71073
0.71073
0.71073
Crystal system
Space group
Unit cell dimensions
monoclinic
P21/c
a ϭ 9.9401(15) A
b ϭ 19.018(3) A
c ϭ 16.783(2) A
orthorhombic
P212121
a ϭ 9.7046(8) A
b ϭ 14.3651(12) A
c ϭ 19.8881(16) A
triclinic
P1
a ϭ 10.0425(11) A
b ϭ 17.9299(18) A
¯
˚
˚
˚
˚
˚
˚
˚
˚
˚
c ϭ 18.2498(19) A
α ϭ 68.821(2)°
β ϭ 88.733(2)°
γ ϭ 89.510(2)°
3063.4(6)
4
β ϭ 90.888(3)°
3
˚
Volume /A
Z
3172.4(8)
4
1.504
2772.6(4)
4
1.449
Density (calculated)
1.480
(Mg/m3)
Absorption coefficient/mm-1
F(000)
0.649
1464
0.726
1240
0.600
1392
Crystal size /mm
Theta range for data collection /°
Index ranges
0.25 x 0.24 x 0.08
1.62 to 28.04
Ϫ13<ϭh<ϭ12;
Ϫ25<ϭk<ϭ25;
Ϫ11<ϭl<ϭ22
20917
0.25 x 0.13 x 0.09
1.75 to 28.03
Ϫ11<ϭh<ϭ12;
Ϫ16<ϭk<ϭ18;
Ϫ26<ϭl<ϭ25
16383
0.67 x 0.47 x 0.14
1.99 to 28.03
Ϫ13<ϭh<ϭ12;
Ϫ23<ϭk<ϭ19;
Ϫ23<ϭl<ϭ23
17962
Reflections collected
Independent reflections
7625
[R(int) ϭ 0.1017]
2564
6318
[R(int) ϭ 0.0752]
2890
12494
[R(int) ϭ 0.0282]
6284
Reflections observed
(>2sigma)
Data Completeness
Refinement method
0.992
0.978
0.841
Full-matrix
Full-matrix
Semi-empirical
from equivalents
12494 / 0 / 793
0.810
least-squares on F2
7625 / 0 / 406
0.675
least-squares on F2
6318 / 0 / 3430
0.696
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices
[I>2sigma(I)]
R indices (all data)
R1 ϭ 0.0455
wR2 ϭ 0.0460
R1 ϭ 0.1830
wR2 ϭ 0.0613
0.368 and Ϫ0.273
R1 ϭ 0.0444
wR2 ϭ 0.0470
R1 ϭ 0.1302
wR2 ϭ 0.0575
0.754 and Ϫ0.358
R1 ϭ 0.0462
wR2 ϭ 0.0756
R1 ϭ 0.1111
wR2 ϭ 0.0883
0.432 and Ϫ0.449
Largest diff. peak and hole
Ϫ3
Ϫ3
Ϫ3
˚
˚
˚
e.A
e.A
e.A
ate was quickly substituted by acetonitrile, and, in more
drastic conditions, by SCN. Formation of the CN complex
was only possible from the corresponding L2 compound.
After maintaining complex 3 for 2 days in CH2Cl2, yel-
lowish crystals were formed. Solid-state structure of the
new compound has been obtained from single-crystal X-ray
structural analysis, revealing the substitution of the CH3CN
ligand by Cl. This displacement was not achieved in the
analogous L2 compound (complex 9).
as expected from the π-donor character of the halogen [e.g.
˚
1.775(4) vs. 1.807(4) and 1.803(4) A in the chloro-, 1.805(7)
˚
vs. 1.835(6) and 1.841(7) A in the bromo-complex]. Simi-
larly, the Mn-C bond lengths for the CO ligands trans to
oxygen are 1.769(4) [vr. 1.823(4), 1.845(4)], 1.770(3) [vr.
˚
1.826(4), 1.851(4)] and 1.743(6) A [vr. 1.814(6), 1.806(6)] for
complexes 1, 5 and 11, respectively. Finally, the Mn-O bond
leads to a lengthening of the corresponding C-O or S-O
distance in the carboxylato or the thiolato group, respec-
tively. For instance, in complex 11: C(4)-O(4) ϭ 1.274(6),
˚
C(4)-O(5) ϭ 1.200(6) A; in complex 1: S-O(11) ϭ 1.467(2),
3.2 Crystal structures
˚
S-O(13) ϭ 1.427(2) A. In the same way, the C-N bond in
CH3CN is slightly weakened upon coordination to the me-
Figures 1Ϫ7 show ORTEP diagrams of the complexes with
the numbering scheme. The crystallographic data are listed
in Tables 1 and 2, and Table 3 lists some selected bond
lengths and angles. In all the complexes the coordination
sphere around the metal atom is a distorted octahedron,
with the three CO ligands in a facial disposition. The Mn-
˚
˚
tal [1.136(4) A vs. 1.158 A in the free acetonitrile] [16].
The bond angles around the Mn range from 82.29(13)°
for C(2)-Mn-Cl in complex 4 to 97.07(3)° for P(1)-Mn-P(2)
in complex 10. In the case of the P-Mn-P angles, the values
are in the range 88.17(3)-97.07(3)° (i.e. very close to 90°),
showing that the number of members of the chelating ring
involved in this bond is great enough to induce no signifi-
cant steric hindrance in the bidentate phosphane ligand.
The possibility of a weak interaction between the donor
atom (Br, O, N) and one H atom of a CH2 group on the
˚
P bond lengths range from 2.3172(10) to 2.3922(10) A, as
found in other similar phosphane manganese(I) complexes
[14], and are smaller than the sum of their covalent radii
˚
(2.49 A) [15], as a consequence of the π interaction. Besides,
the CO ligands trans to Br or Cl are closer to the Mn atom,
2070
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Tricarbonyl Derivatives of Manganese(I) with Diphosphinite Chelating Ligands
Table 2 Crystal data and structure refinement details for complexes 6, 9Ϫ11.
6
9
10
11
Empirical formula
Formula weight
Temperature /K
C17H28BrMnO5P2
509.18
293(2)
C20H35F3MnNO8P2S
623.43
293(2)
C18H32MnNO5P2
459.33
293(2)
C19H32F3MnO7P2
546.33
293(2)
˚
Wavelength /A
0.71073
0.71073
0.71073
0.71073
Crystal system
Space group
Unit cell dimensions
monoclinic
P21/n
a ϭ 14.3682(13) A
b ϭ 9.7777(9) A
c ϭ 16.6255(15) A
triclinic
P1
a ϭ 9.9943(9) A
b ϭ 11.0134(10) A
c ϭ 13.9877(14) A
monoclinic
P21/n
a ϭ 14.5291(15) A
b ϭ 9.7884(10) A
c ϭ16.3802(17) A
monoclinic
P21/c
a ϭ 9.3296(10) A
b ϭ 16.3474(18) A
c ϭ 17.1995(18) A
¯
˚
˚
˚
˚
˚
˚
˚
˚
˚
˚
˚
˚
α ϭ 71.415(2)°
β ϭ 89.605(2)°
γ ϭ 84.980(2)°
1453.4(2)
2
β ϭ 103.987(2)°
β ϭ 104.369(2)°
β ϭ 93.409(2)°
3
˚
Volume /A
Z
2266.4(4)
4
1.492
2256.7(4)
4
1.352
2618.5(5)
4
1.386
Density (calculated)
1.425
/(Mg/m3)
Absorption coefficient
/mmϪ1
F(000)
2.509
0.696
0.753
0.681
1040
648
968
1136
Crystal size /mm
Theta range for
data collection /°
Index ranges
0.24 x 0.21 x 0.14
1.68 to 28.07
1.00 x 0.41 x 0.10
1.96 to 28.02
0.48 x 0.36 x 0.19
1.68 to 27.99
0.52 x 0.28 x 0.07
1.72 to 28.11
Ϫ18<ϭh<ϭ18,
Ϫ8<ϭk<ϭ12,
Ϫ22<ϭl<ϭ21
Ϫ12<ϭh<ϭ13;
Ϫ14<ϭk<ϭ12;
Ϫ15<ϭl<ϭ18
Ϫ18<ϭh<ϭ18;
Ϫ12<ϭk<ϭ12;
Ϫ14<ϭl<ϭ21
Ϫ12<ϭh<ϭ12;
Ϫ19<ϭk<ϭ21;
Ϫ22<ϭl<ϭ16
Reflections collected
Independent reflections
12455
5082
8641
6036
13061
5152
14079
5805
[R(int) ϭ 0.0647]
[R(int) ϭ 0.0221]
3729
[R(int) ϭ 0.0526]
3343
[R(int) ϭ 0.0568]
2049
Reflections observed
(>2sigma)
Data Completeness
Refinement method
0.925
0.858
0.948
0.906
Full-matrix least-squares
Full-matrix least-squares
Full-matrix least-squares
Full-matrix least-squares
on F2
on F2
on F2
on F2
Data/restraints/ parameters
Goodness-of-fit on F2
Final R indices
[I>2sigma(I)]
R indices (all data)
5082 / 0 / 243
0.831
R1 ϭ 0.0555,
wR2 ϭ 0.1247
R1 ϭ 0.1445,
wR2 ϭ 0.1442
6036 / 0 / 334
0.910
R1 ϭ 0.0524
wR2 ϭ 0.1254
R1 ϭ 0.0844
wR2 ϭ 0.1365
5152 / 0 / 252
0.894
R1 ϭ 0.0423
wR2 ϭ 0.0838
R1 ϭ 0.0771
wR2 ϭ 0.0914
5805 / 0 / 297
0.813
R1 ϭ 0.0583
wR2 ϭ 0.1223
R1 ϭ 0.2028
wR2 ϭ 0.1537
Ϫ3
Ϫ3
Ϫ3
Ϫ3
˚
˚
˚
˚
Largest diff. peak and hole
0.643 and Ϫ0.729 e.A
0.483 and Ϫ0.368 e.A
0.468 and Ϫ0.368 e.A
0.395 and Ϫ0.293 e.A
Scheme 1
bidentate ligand could also be considered in some cases. For
the case of complex 1, the interaction between the O atom
instance, in the case of complex 6, the Br...H distance
of the triflate ligand and one of the CH2 groups is less prob-
˚
˚
(2.80 A) for one of the conformational isomers (see Fig. 8)
able since the O...H distance (2.67 A) takes almost the same
˚
˚
is shorter than the sum of the van der Waals radii (3.0 A),
value as the sum of the v.d.W. radii (2.7 A). In consequence,
so that this conformer could result favoured (i.e., of lower
energy) with respect to the other one. On the contrary, in
the energy gap between both conformers would be smaller
in this case.
Z. Anorg. Allg. Chem. 2005, 631, 2067Ϫ2074
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© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
2071

´
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J. Bravo, J. A. Castro, E. Freijanes, S. GarcıaϪFontan, E. M. Lamas, P. Rodrıguez-Seoane
Scheme 2
Table 3 Selected bond lengths/A and angles/° for the complexes
˚
1
4
5
6
9
10
11
Mn-C(1)
Mn-C(2)
Mn-C(3)
Mn-O
1.769(4)
1.823(4)
1.845(4)
2.082(2)
1.775(4)
1.807(4)
1.803(4)
Ϫ
1.770(3)
1.776(3)
1.826(4)
1.828(3)
1.851(4)
1.844(4)
2.045(2)
2.0481(19)
Ϫ
1.803(7)
1.835(6)
1.841(7)
Ϫ
1.799(4)
1.829(4)
1.818(4)
Ϫ
1.803(3)
1.825(3)
1.812(3)
Ϫ
1.743(6)
1.814(6)
1.806(6)
2.046(3)
Mn-Cl
Ϫ
2.4284(11)
Ϫ
Ϫ
Ϫ
Ϫ
Mn-Br
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
2.5286(11)
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Mn-N(1)
Mn-C(4)
N(1)-C(4)
Mn-P(1)
2.017(3)
Ϫ
1.136(4)
2.3782(10)
1.992(3)
1.146(3)
2.3626(8)
2.3208(10)
2.3275(11)
2.3172(10)
2.3222(10)
2.3364(11)
2.3351(9)
1.160(3)
1.160(3)
1.140(4)
1.139(3)
1.143(4)
1.132(4)
2.3720(16)
2.3617(15)
Mn-P(2)
2.3673(10)
1.155(4)
1.146(4)
1.147(3)
2.3234(11)
1.143(4)
1.153(4)
1.155(4)
2.3531(17)
1.093(6)
1.123(6)
1.049(6)
2.3922(10)
1.144(4)
1.143(4)
1.141(4)
2.3365(8)
1.157(3)
1.136(3)
1.152(3)
2.3559(15)
1.173(5)
1.144(5)
1.146(5)
C(1)-O(1)
C(2)-O(2)
C(3)-O(3)
S-O(11)
S-O(13)
C(4)-O(4)
C(4)-O(5)
C(2)-Mn-Cl
P(1)-Mn-P(2)
1.467(2)
1.427(2)
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
1.274(6)
1.200(6)
Ϫ
82.29(13)
88.29(4)
89.75(4)
91.11(4)
88.17(3)
96.70(6)
94.93(3)
97.07(3)
93.44(5)
3.3 Spectroscopic results
for complexes 1 and 7, respectively). Finally, in the spectra
of the trifluoroacetate complexes, the singlet occurs at δ ഠ
Ϫ75 (Ϫ74.7 and Ϫ75.1 for 5 and 11, respectively).
The signal of 31P{1H} NMR spectrum is in all cases a
singlet, showing the magnetic equivalence of both P atoms
of each bidentate ligand at room temperature.
All the synthesized complexes show, in the IR spectrum, 3
strong bands in the carbonyl-stretching region, in a pattern
that is characteristic of a fac-octahedral disposition, and at
values of wave number similar to that found in other Mn
complexes with analogous P coligands [17].
The 19F{1H} NMR spectra of the fluor-containing com-
pounds show all of them a singlet, which is located at about
δ ϭ Ϫ79 in the case of complexes bearing the O3SCF3
anion out of the coordination sphere (Ϫ79.0 and Ϫ79.4 for
complexes 3 and 9, respectively). When this anion is coordi-
nated to manganese, the signal is, as expected, slightly
shifted downfield, namely at δ ഠ Ϫ77 (Ϫ77.3 and Ϫ77.5
Regarding the 1H NMR spectra, all of them show, at
about 4 ppm, the signals attributable to the CH2 groups of
the bidentate ligand. Nevertheless, whereas the spectra of
most of the complexes show two multiplets (at 4.13Ϫ4.54
and 3.84Ϫ4.14 ppm, respectively), in three of them both
signals coalesce into one multiplet (at 4.07, 4.04 and
4.20 ppm for complexes 1, 7 and 9, respectively). The com-
2072
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
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Z. Anorg. Allg. Chem. 2005, 631, 2067Ϫ2074

Tricarbonyl Derivatives of Manganese(I) with Diphosphinite Chelating Ligands
Fig. 4 Displacement ellipsoid plot for complex 6 with the atom
numbering scheme. Ellipsoids at 30 % probability.
Fig. 1 Displacement ellipsoid plot for complex 1 with the atom
numbering scheme. Ellipsoids at 30 % probability.
Fig. 5 Displacement ellipsoid plot for the cation of complex 9 with
the atom numbering scheme. Ellipsoids at 30 % probability.
Fig. 2 Displacement ellipsoid plot for complex 4 with the atom
numbering scheme. Ellipsoids at 30 % probability.
Fig. 6 Displacement ellipsoid plot for complex 10 with the atom
numbering scheme. Ellipsoids at 30 % probability.
plexes showing the more complicated spectra are the same
that bear in the solid state the supposed C-H...X interaction
commented above. Despite this coincidence, no relationship
between both facts seems to be supported by the 13C{1H}
Fig. 3 Displacement ellipsoid plot for one of the two molecules of
the asymmetric unit for complex 5 with the atom numbering
scheme. Ellipsoids at 30 % probability.
Z. Anorg. Allg. Chem. 2005, 631, 2067Ϫ2074
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© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
2073

´
´
´
J. Bravo, J. A. Castro, E. Freijanes, S. GarcıaϪFontan, E. M. Lamas, P. Rodrıguez-Seoane
Fig. 8 Chelate ring showing the Br...HCH interaction.
[6] T. K. Hollis, W. Odenkirk, N. P. Robinson, J. Whelan, B. Bos-
nich, Tetrahedron 1993, 49, 5415.
´
´
´
[7] J. Bravo, J. Castro, S. Garcıa-Fontan, E. M. Lamas, P. Rodrı-
guez-Seoane, Z. Anorg. Allg. Chem. 2003, 629, 297.
[8] D. D. Perrin, W. L. F. Amarego, Purification of Laboratory
Chemicals, 3rd. ed., Butterworth and Heinemann, Oxford,
1988.
´
´
[9] S. Bolan˜o, J. Bravo, R. Carballo, S. Garcıa-Fontan, U. Abram,
Fig. 7 Displacement ellipsoid plot for complex 11 with the atom
numbering scheme (isopropyl groups are omitted for clarity).
Ellipsoids at 30 % probability.
´
´
E. M. Vazquez-Lopez, Polyhedron 1999, 18, 1431.
[10] E. W. Abel, G. Wilkinson. J. Chem. Soc. 1959, 1501.
[11] G. M. Sheldrick, SADABS, An Empirical Absorption Correc-
tion Program for Area Detector Data, University of
Göttingen, Germany, 1996.
[12] G. M. Sheldrick, SHELXLϪ97, A Program for the Refine-
ment of Crystal Structures from X-ray Data, University of
Göttingen, Germany, 1997.
NMR spectra, which show for both C nuclides one single
signal in all cases.
[13] L. J. Farrugia, J. Appl. Cryst. 1997, 30, 565.
[14] T. M. Becker, J. A. Krause-Bauer, C. L. Homrighausen, M.
Orchin, Polyhedron 1999, 18, 2563.
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[1] See for instance: (a) R. V. Honeychuck, W. H. Hersh, Inorg.
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[2] G. A. Lawrence, Chem. Rev. 1986, 86, 17.
[3] D. Veghini, H. Berke, Inorg. Chem. 1996, 35, 4770.
[4] P. Bergamini, F. Fabrizi DeBiani, L. Marvelli, N. Mascellani,
M. Peruzzini, R. Rossi, P. Zanello, New J. Chem. 1999, 207.
[5] T. K. Hollis, N. P. Robinson, B. Bosnich, Organometallics
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[15] J. E. Huheey, E. A. Keiter, R. L. Keiter, Inorganic Chemistry.
Principles of Structure and Reactivity, 4th. ed., Harper-Collins
College Publishers, New York, 1993.
[16] A. F. Wells, Structural Inorganic Chemistry, 5th. ed., Oxford
University Press, 1993.
´
´
[17] G. Albertin, S. Antoniutti, S. Garcıa-Fontan, R. Carballo, F.
Padoan, J. Chem. Soc., Dalton Trans. 1998, 2071.
2074
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