Use of the aqua complex [fac-Mn(CO)3(dppe)OH2]BF4 for the preparation of a series of fac-Mn(CO)3(dppe)Z and [fac-Mn(CO)3(dppe)Z]BF4 complexes. X-ray crystal structures of three representative examples

Article abstract of DOI:10.1016/S0022-328X(00)00130-3

The aqua ligand in the titled complex (prepared by a simple two-step, high-yield synthesis) is readily replaced by the desired anionic ligand Z^-, to give a six-coordinate neutral species fac-Mn(CO)₃(dppe)Z. Examples of such complexes where Z=O-NO₂, CN, OMe, OC(O)OMe, and OS(O)₂CF₃ (OTf) are reported herein. Neutral ligands also replace the aqua ligand to give ionic complexes [fac-Mn(CO)₃(dppe)Z]BF₄. Examples where Z=2,6-dimethylphenyl (xylyl) isocyanide, acetonitrile, benzonitrile, and acrylonitrile are also reported herein. Crystal structures of fac-Mn(CO)₃(dppe)NO₃ (2), [fac-Mn(CO)₃(dppe)(xylyl-NC)]BF₄ (7), and [fac-(CO)₃Mn(dppe)(PhCN)]BF₄ (9), are reported.

Full text of DOI:10.1016/S0022-328X(00)00130-3

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 602 (2000) 97–104
Use of the aqua complex [ fac-Mn(CO)3(dppe)OH2]BF4 for the
preparation of a series of fac-Mn(CO)3(dppe)Z and
[ fac-Mn(CO)3(dppe)Z]BF4 complexes. X-ray crystal structures of
three representative examples
Thomas M. Becker, Jeanette A. Krause Bauer, Craig L. Homrighausen,
Milton Orchin *
Department of Chemistry, Uni6ersity of Cincinnati, PO Box 210172, Cincinnati, OH 45221-0172, USA
Received 11 November 1999; received in revised form 17 February 2000
Abstract
The aqua ligand in the titled complex (prepared by a simple two-step, high-yield synthesis) is readily replaced by the desired
anionic ligand Z−, to give a six-coordinate neutral species fac-Mn(CO)3(dppe)Z. Examples of such complexes where ZꢀOꢁNO2,
CN, OMe, OC(O)OMe, and OS(O)2CF3 (OTf) are reported herein. Neutral ligands also replace the aqua ligand to give ionic
complexes [ fac-Mn(CO)3(dppe)Z]BF4. Examples where Z=2,6-dimethylphenyl (xylyl) isocyanide, acetonitrile, benzonitrile, and
acrylonitrile are also reported herein. Crystal structures of fac-Mn(CO)3(dppe)NO3 (2), [ fac-Mn(CO)3(dppe)(xylyl-NC)]BF4 (7),
and [ fac-(CO)3Mn(dppe)(PhCN)]BF4 (9), are reported. © 2000 Elsevier Science S.A. All rights reserved.
Keywords: Manganese complexes; Crystal structures; Nitrato complexes; Isocyanide complexes; Nitrile complexes
1. Introduction
from Pressure Chemicals. [Fac-Mn(CO)3(dppe)-
(OH2)]BF4 (1), and fac-Mn(CO)3Mn(dppe)H were pre-
pared by methods described in the literature [1,2]. Tri-
fluoromethanesulfonic (triflic) acid was purchased from
Aldrich. IR spectra were recorded on a Perkin–Elmer
Spectrum One FT-IR instrument employing 1.0 mm
NaCl liquid cells unless noted otherwise. 1H-NMR data
were recorded using a Bruker AC-250 spectrometer
with CDCl3 chemical shifts recorded relative to Me4Si.
Melting points were obtained using a Mel-Temp ap-
paratus and are uncorrected. Elemental analyses were
performed by Galbraith Laboratories and Chemisar
Laboratories. Mass spectra were recorded on a Kratos
MS-890 high-performance mass spectrometer. The pu-
rity of each of the new compounds was assured by
careful examination of the spectroscopic data (particu-
The aqua complex [ fac-Mn(CO)3(dppe)(OH2)]BF4
(1), [1] provides a convenient starting compound en-
route to manganese complexes possessing a wide vari-
ety of functional groups directly s-bonded to the metal.
Treatment of the aqua complex 1, with anionic species
Z− leads to neutral, six-coordinate complexes with Z
s-bonded to the metal. Products corresponding to sim-
ple anion exchange were not observed. Neutral ligands
Z, also react with 1 producing complexes of the type,
[ fac-Mn(CO)3(dppe)Z]BF4.
2. Experimental
1
larly H-NMR) and by thin-layer chromatography.
All reactions were carried out under an argon atmo-
sphere using a Schlenk line. Solvents were used as
received unless otherwise noted. Dppe was purchased
2.1. Preparation of fac-(CO)3Mn(dppe)OꢁNO2 (2)
The aqua complex 1 (86 mg, 0.13 mmol) was added
* Corresponding author. Fax: +1-513-5569239.
to a round bottomed flask and dissolved in approxi-
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 0 ) 0 0 1 3 0 - 3

98
T.M. Becker et al. / Journal of Organometallic Chemistry 602 (2000) 97–104
1
mately 15 ml of CHCl3. Excess KNO3 (aq.) (1 ml of a
saturated solution) was added and the mixture stirred
for 4.5 h. All liquids were removed via rotary evapora-
tion. The residue was stirred with CH2Cl2 and then
filtered to remove excess KNO3 and KBF4. The CH2Cl2
was removed by rotary evaporation. The addition of
hexane, followed by rotary evaporation yielded the
yellow solid 2 (72 mg, 90% yield). X-ray quality crystals
were grown from CH2Cl2–hexane.
1920 s. H-NMR (l, CDCl3): 7.67–7.35 (m, 20H, Ph),
3.96–3.62 (m, 4H, CH2) MS (m/z): 537
([Mn(CO)3(dppe)]+), 453 ([Mn(dppe)]+). Anal. Calc.
for C30H24MnNO3P2: H, 4.3; N, 2.5. Found: H, 4.4; N,
2.5%. Carbon analysis was unsatisfactory.
2.3. Preparation of fac-(CO)3Mn(dppe)OMe (4) and
fac-(CO)3Mn(dppe)OC(O)OMe (5)
Data 2: decomposition occurs at 168–170°C. IR
(cm−1, CHCl3): w(CꢂO) 2034 s, 1968 s, 1925 s.
1H-NMR (l, CDCl3): 7.6–7.3 (m, 20H, Ph), 3.0–2.7
(m, 4H, CH2) MS (m/z): 515 ([Mn(dppe)NO3]+), 453
([Mn(dppe)]+). Anal. Calc. for C29H24MnNO6P2·1/
4H2O: C, 57.7; H, 4.09; N, 2.32. Found: C, 57.2; H,
4.05; N, 2.28% (see Fig. 1 for crystal structure).
The aqua complex 1 (114 mg, 0.178 mmol) was
placed in a round-bottomed flask and 7.78 ml of freshly
prepared 0.228 M NaOMe (prepared from 0.52g of Na
dissolved in 99 ml of methanol) was added. Additional
methanol was added to bring the total amount of
solution to approximately 15 ml and the solution was
stirred for 3 h 15 min and then rotovaped to yield 4
plus a small amount of 5 as indicated by IR spec-
troscopy [3,4]. The mixture 4 was converted completely
to 5 by exposure to CO2 (86 mg, 79% yield). The
spectroscopic data agreed with that reported previously
for 5 [4].
2.2. Preparation of fac-(CO)3Mn(dppe)CN (3)
The aqua complex 1 (101 mg, 0.157 mmol) was
dissolved in about 15 ml of CHCl3. A total of 20 drops
of a saturated KCN (aq.) solution were added and the
mixture stirred for 1 h 35 min. The solvents were
removed by rotary evaporation and the residue vacuum
dried to ensure water removal. The solid material was
dissolved in CH2Cl2 and filtered to remove KBF4 and
excess KCN. Removal of CH2Cl2 yielded the yellow
solid 3 (51 mg, 58% yield).
2.4. Preparation of fac-Mn(CO)3(dppe)OTf (6)
The aqua complex 1 (83 mg, 0.13 mmol) was dis-
solved in about 15 ml of CHCl3. Excess triflic acid
(0.050 ml, 0.57 mmol) was added via syringe and the
mixture was stirred for 3 h. The solution was extracted
with water to remove any excess acid and the CHCl3
was removed via rotary evaporation. The residue was
Data 3: decomposition occurs at 174–177°C. IR
(cm−1, CHCl3): w(CꢂN) 2242m, w(CꢂO) 2030 s, 1960 s,
Fig. 1. ORTEP diagram of fac-Mn(CO)3(dppe)NO3 (2), indicating labeling scheme and 50% thermal ellipsoids.

T.M. Becker et al. / Journal of Organometallic Chemistry 602 (2000) 97–104
99
dissolved in CH2Cl2–hexane and the solvent removed
via rotary evaporation, giving 6 as a yellow solid (89
mg, 100% yield).
Data 8: decomposition occurs at 110–114°C. IR
(cm−1, CHCl3): w(CꢂN) 2286 vw, w(CꢂO) 2039 s, 1970
1
s, 1952 s. H-NMR (l, acetone-d): 8.04–7.7 (m, 20H,
Data 6: decomposition occurs at 169–171°C. IR
(cm−1, CHCl3): w(CꢂO) 2040 s, 1974 s, 1928 s. 1H-
NMR (l, CDCl3): 7.65–7.30 (m, 20H, Ph), 3.00–2.79
(m, 4H, CH2) MS (m/z): 537 ([Mn(CO)3(dppe)]+), 453
([Mn(dppe)]+). Anal. Calc. for C30H24F3MnO6P2S: C,
52.5; H, 3.52; S, 4.67. Found: C, 52.8; H, 3.78; S,
4.81%.
Ph), 3.6–3.2 (m, 4H, CH2), 1.72 (s, 3H, CH3) MS
(m/z):
578
([Mn(CO)3(dppe)(CH3CN)]+),
537
([Mn(CO)3(dppe)]+), 453 ([Mn(dppe)]+). Anal. Calc.
for C31H27BF4MnNO3P2: C, 56.0; H, 4.09; N, 1.8.
Found: C, 55.4; H, 4.05; N, 1.8%.
2.8. Preparation of [fac-(CO)3Mn(dppe)(PhCN)]BF4 (9)
The aqua complex 1 (103 mg, 0.161 mmol) was
dissolved in approximately 15 ml of CHCl3. Benzoni-
trile (0.050 ml, 0.49 mmol) was added via syringe and
the mixture was stirred for 20 min during which time
the color of the yellow solution faded significantly. The
chloroform was removed by rotary evaporation. The
residue was stirred with hexane (8×2 ml) to dissolve
excess benzonitrile. The remaining hexane was removed
via rotary evaporator giving the pale yellow solid 9 (102
mg, 87% yield). X-ray quality crystals were obtained
from CH2Cl2–hexane.
2.5. Alternati6e preparation of fac-Mn(CO)3(dppe)OTf
(6) from fac-Mn(CO)3(dppe)H
The hydride, fac-Mn(CO)3(dppe)H (220 mg, 0.409
mmol), was dissolved in about 15 ml of CHCl3. A slight
excess of triflic acid (0.050 ml, 0.57 mmol) was added
via syringe. Evolution of H2 occurred immediately and
the reaction was stirred for 2 h. The workup of the
reaction mixture was conducted in a manner identical
to the isolation of 6 described above; (272 mg, 97%
yield).
Data 9: m.p. 172–173°C. IR (cm−1, CHCl3): w(CꢂN)
1
2254 vw, w(CꢂO) 2038 s, 1969 s, 1957 s. H-NMR (l,
2.6. Preparation of
[fac-(CO)3Mn(dppe)(xylylꢁNꢂC)]BF4 (7)
CDCl3): 7.8–6.55 (m, 25H, Ph), 3.7–3.0 (m, 4H, CH2).
MS (m/z): 640 ([Mn(CO)3(dppe)(PhCN)]+), 537
([Mn(CO)3(dppe)]+), 453 ([Mn(dppe)]+). Anal. Calc.
for C36H29BF4MnNO3P2·1/2H2O: C, 58.7; H, 4.11.
Found: C, 58.8; H 4.20%.
The aqua complex 1 (220 mg, 0.343 mmol) was
dissolved in approximately 15 ml of CHCl3. Excess
xylyl isocyanide (76 mg, 0.58 mmol) was added and the
mixture was stirred for 25 min. The solvent was re-
moved via rotary evaporation. Hexane was added, the
mixture stirred and the hexane solution was decanted
(4×3 ml), thereby removing excess isocyanide. Hexane
was added again and removed via rotary evaporation
yielding the white solid 7 (230 mg, 89% yield). X-ray
quality crystals were obtained from CH2Cl2–hexane.
Data 7: m.p. 240–243°C. IR (cm−1, CHCl3): w(CꢂN)
2.9. Preparation of
[fac-(CO)3Mn(dppe)(CH2ꢀCHCN)]BF4 (10)
The aqua complex 1 (1.461 g, 2.278 mmol) was
dissolved in approximately 50 ml of CHCl3. Acryloni-
trile (3.0 ml, 45 mmol) was added via syringe and the
mixture was stirred for 2 h during which time the color
of the yellow solution faded significantly. The mixture
was rotovaped to remove chloroform and excess acry-
lonitrile. A mixture of CH2Cl2–hexane was added and
then removed via rotary evaporator yielding the pale
yellow solid 10 (1.436 g, 93% yield).
1
2151 m, w(CꢂO) 2035 s, 1982 s, 1973 s. H-NMR (l,
CDCl3): 7.8–6.8 (m, 23H, Ph), 3.6–3.1 (m, 4H, CH2),
1.62 (s, 6H, CH3). MS (m/z): 668 ([Mn(CO)3-
(dppe)(xylylꢁNC)]+), 584 ([Mn(dppe)(xylylꢁNC)]+),
453 ([Mn(dppe)]+). Anal. Calc. for C38H33BF4-
MnNO3P2: C, 60.4; H, 4.40. Found: C, 60.0; H 4.39%.
Data 10: m.p. (dec.) occurs at 82–86°C. IR (cm−1
,
CHCl3): w(CꢂN) 2257 vw, w(CꢂO) 2038 s, 1971 s, 1957
1
s. H-NMR (l, CDCl3): 7.8–7.2 (m, 20H, Ph), 5.87 [d,
2.7. Preparation of
1H, Hcis, J(Hcis–Hgem)=12 Hz], 5.45 [d, 1H, Htrans,
[fac-(CO)3Mn(dppe)(CH3CN)]BF4 (8)
J(Htrans–Hgem)=18 Hz], 5.03 (dd, 1H, Hgem), 3.65–
2.85 (m, 4H, CH2). MS (m/z): 590 ([Mn(CO)3-
(dppe)(CH2ꢀCHCN)]+), 537 ([Mn(CO)3(dppe)]+), 453
([Mn(dppe)]+). Anal. Calc. for C32H27BF4MnNO3P2:
C, 56.7; H, 4.0. Found: C, 56.3; H 4.4%.
The aqua complex 1 (148 mg, 0.230 mmol) was
dissolved in approximately 15 ml of CHCl3. Acetoni-
trile (0.060 ml, 1.1 mmol) was added via syringe and the
mixture was stirred for 2 h during which time the color
of the yellow solution faded significantly. The mixture
was rotovaped yielding an oil, which was then stirred
with hexane. Rotary evaporation of the hexane yielded
the pale yellow solid 8 (133 mg, 87% yield).
2.10. X-ray diffraction studies of 2, 7, and 9
Crystals of 2, 7, and 9 used for the X-ray diffraction
experiments were grown from CH2Cl2–hexane. When

100
T.M. Becker et al. / Journal of Organometallic Chemistry 602 (2000) 97–104
attempts were made to cut crystals of 7, they shattered
and hence a larger than desirable crystal was used for
the experiment. The crystals of 2 and 9 were of a more
desirable size, namely less than 0.5 mm on an edge. All
crystals were mounted on the tip of a glass fiber with
epoxy resin.
refinement. A water molecule (0.5 total occupancy) is
found in the crystalline lattice for 7. The water oxygen
in 7 appears disordered over two positions with the
H-atoms shared between them. The anisotropic dis-
placement parameter for O1WB was constrained to be
equal to that of O1WA, otherwise OW1B had a ten-
dency to be non-positive definite. The BF4 anion in 7 is
disordered with two major conformers located (occu-
pancy set at 0.5 for F2–F4 and 1.0 for F1). The
refinement of BF4 did not proceed without difficulty;
several restraints on bond distances and magnitude of
displacement parameters were necessary. The BF4 an-
ion in 9 also shows disorder in two of the fluorines
(occupancy set at 0.5 for F3 and F4). The refinements
for all structures converged with crystallographic agree-
ment factors summarized in Table 1.
Intensity data for 7 were collected at 21°C on a
Siemens P3 diffractometer [5] with graphite-monochro-
mated Mo Ka radiation. Intensity data were collected
using variable q−2q scans in ꢀ out to a maximum q
value of 27.56°. The data were processed using the
program XDISK. The data were corrected for decay,
Lorentz and polarization effects as well as absorption
(based on measured c scans). A hemisphere of intensity
data for 2 were collected at 150 K on a Siemens SMART
2K CCD diffractometer [6] using graphite-monochro-
mated Ag Ka radiation, a detector distance of 3.905 cm
from the crystal, 25-s frames at 0.3° intervals of ꢀ, and
a maximum q value of 22.09°. A hemisphere of inten-
sity data for 9 were collected at 175 K on a Siemens
SMART 1K CCD diffractometer using graphite-
monochromated Mo Ka radiation, a detector distance
of 5.010 cm and 30-s frames at 0.3° intervals of ꢀ and
a maximum q value of 28.26°. The CCD data frames
were processed using the program SAINT. All data were
corrected for decay, Lorentz and polarization effects as
well as absorption (based on the multi-scan technique
using SADABS [7]).
All structures were solved by a combination of direct
methods using SHELXTL version 5.03 [8] and the differ-
ence Fourier technique and refined by full-matrix least-
squares on F2 [9]. Non-hydrogen atoms were refined
with anisotropic displacement parameters. Weights
were assigned as w−1=|2(F2o)+(aP)2+bP where P=
0.33333F2o+0.66667F2c and a=0.0560, b=0.00 for 2,
a=0.0786, b=1.4909 for 7, and a=0.0281, b=
33.6397 for 9. Positions of the hydrogen atoms for 7
were either calculated (based on geometric criteria) or
located directly from the difference map. A riding
model was imposed on the H-atom positions in subse-
quent refinements. For 2, all H-atom positions on the
chelated phosphine were calculated and treated with a
riding model in the refinements. H1W was located
directly from the difference map while H2W was calcu-
lated, based on hydrogen bonding distances from the
water to the manganese complex. The H-atom positions
on the water were held fixed. All aromatic and
methylene H-atom positions in 9 were calculated and
treated with a riding model in the refinements. H1W
and H2W were located directly from the difference map
and held fixed in subsequent refinements. In all cases,
hydrogen atom isotropic temperature factors were
defined as a*Ueq of the adjacent atom where a=1.5 for
CH3 and OH and 1.2 for all others.
3. Results and discussion
The one-pot synthesis of fac-Mn(CO)3(dppe)H from
Mn2(CO)10 and dppe in refluxing 1-pentanol [2], fol-
lowed by its subsequent reaction with HBF4, provides
an easy two step route to the aqua complex 1 [1]. The
general reactions in chloroform at room temperature
(r.t.) to produce neutral complexes of the type; fac-
Mn(CO)3(dppe)Z and ionic complexes of the type;
[ fac-Mn(CO)3(dppe)Z]BF4 are depicted in Eq. (1) Eq.
(2), respectively.
(1)
(2)
The triflato complex, 6, was also prepared from the
reaction of the hydride, fac-Mn(CO)3(dppe)H, with an
excess of triflic acid. Immediate hydrogen gas evolution
was observed and 6 was separated from excess acid and
isolated in quantitative yield.
The progress of these reactions was followed by IR
spectroscopy. The IR spectra of complexes 2–10 exhibit
three strong carbonyl bands consistent with a facial
carbonyl arrangement. Complexes 3 and 7 have a
In 2 the occupancy of the water molecule refined to
nearly 0.25 and was fixed at this value in the final
medium intensity CꢂN band at 2242 and 2151 cm−1
,

T.M. Becker et al. / Journal of Organometallic Chemistry 602 (2000) 97–104
101
Table 1
Crystal data and structure refinement for 2, 7 and 9
2
7
9
Empirical formula
Formula weight
Temperature (K)
C29H24NO6P2Mn·0.25(H2O)
603.88
150(2)
[C38H33MnNO3P2]BF4
755.34
294(2)
[C36H29NO3P2Mn]BF4·0.5(H2O)
736.30
175(2)
,
Wavelength (A)
0.56086
Monoclinic
P21/n
0.71073
Triclinic
0.71073
Monoclinic
C2/c
Crystal system
Space group
Unit cell
(
P1
,
a (A)
12.9745(14)
14.3516(14)
15.327(2)
10.987(2)
12.906(3)
14.188(3)
78.99(3)
67.83(3)
86.89(3)
1828.5(6)
2
24.440(3)
12.819(1)
21.836(2)
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
105.945(5)
100.504(2)
3
,
V (A )
2744.1(5)
4
1.462
0.338
6726.4
8
1.454
0.549
Z
zcalc (Mg m−3
)
1.372
0.506
v (mm−1
)
Tmin/Tmax
0.8495/0.8769
0.7576/0.9194
0.8102/0.8749
F(000)
1242
776
3016
qmax (°)
22.09
27.56
28.26
Independent reflections
6888
8450
8172
Rint
0.0989
0.0159
0.1215
Data/parameters
S
6887/361
0.979
8391/466
1.023
6819/463
1.101
R indices [I\2|(I)]
R1=0.0459, wR2=0.1007
R1=0.0889, wR2=0.1199
0.687
R1=0.0532, wR2=0.1437
R1=0.0947, wR2=0.2154
0.952
R1=0.0685, wR2=0.1197
R1=0.1566, wR2=0.1623
0.394
R indices (all data)
−3
,
Residual peak (e A
)
neutral and cationic manganese complexes from it, thus
allowing access to complexes having a variety of func-
tional groups s-bonded to the manganese atom.
respectively. The IR spectra of the nitriles 8–10 display
very weak CꢂN stretches between 2286 and 2254 cm−1
.
1
The H-NMR spectra of all the complexes are rela-
tively straightforward, displaying multiplets in the
phenyl region as well as multiplets in the methylene
region associated with the chelating dppe ligand. The
1H-NMR spectra of complexes 7 and 8 show methyl
3.1. Molecular structures of 2, 7, and 9
Crystallographic data for complexes 2, 7, and 9 are
summarized in Table 1. The molecular structures of 2,
7, and 9 are shown in Figs. 1–3, respectively.
Selected bond distances and angles for the nitrato
complex 2 are found in Table 2. To our knowledge, this
is the first crystal structure of a manganese carbonyl
complex containing a nitrato ligand. The complex crys-
tallizes with 1/4H2O in the lattice and exhibits OꢁH···O
hydrogen bonding. The NO3 ligand is bound terminally
signals at 1.62 and 1.72 ppm, respectively. The Htrans
,
Hcis, and Hgem protons of the acrylonitrile ligand appear
as a doublet, a doublet and a doublet of doublets,
1
respectively, in the 250 MHz H-NMR spectrum. Ap-
parently, J(Hcis–Htrans) is very small and accordingly,
only doublets are observed for Hcis and Htrans in 10.
The mass spectra of complexes 7–10 exhibit molecu-
lar ion peaks as well as the expected fragmentation
peaks. The molecular ion peaks in the mass spectra of
complexes 2, 3, and 6 are not observed; however,
appropriate fragmentation peaks are found.
,
to Mn through O(4) at a distance of 2.050(2) A. The
,
complex has a O(4)ꢁN distance of 1.300(3) A and a
MnꢁO(4)ꢁN bond angle of 123.8(2)°. These distances
and angles are consistent with those of other non-car-
bonyl manganese complexes containing a terminal ni-
trato group [10–12].
Selected bond distances and angles for the isocyanide
complex 7 are found in Table 3. A distance of 1.916(3)
The methoxide complex 4 has been prepared previ-
ously and has been shown to insert CO2 readily upon
exposure to air [3]. The formation of the methoxide
complex 4 was verified (without isolation) by IR spec-
troscopy and it was then converted in situ to the stable
carbonato complex 5.
,
The versatility of the readily available aqua complex
1 has been demonstrated by the ease of creating both
A is found for the manganeseꢁxylyl isocyanide carbon
bond. The CꢂN bond length is 1.154(3) A and the bond
,

102
T.M. Becker et al. / Journal of Organometallic Chemistry 602 (2000) 97–104
Selected bond distances and angles for the benzo-
nitrile complex 9 are given in Table 4. The complex
crystallizes with 1/2H2O in the lattice and exhibits
OꢁH···F and CꢁH···O hydrogen bonds. This latter type
angle for Mn(1)ꢁC(4)ꢁN(1) is 177.4(2)°, demonstrating
a linear linkage as expected. These distances and angles
are consistent with those of other manganese isocyanide
complexes [13–17].
Fig. 2. ORTEP diagram of [ fac-Mn(CO)3(dppe)(xylylꢁNC)]BF4 (7), indicating labeling scheme and 50% thermal ellipsoids.
Fig. 3. ORTEP diagram of [ fac-(CO)3Mn(dppe)(PhCN)]BF4 (9), indicating labeling scheme and 50% thermal ellipsoids.

T.M. Becker et al. / Journal of Organometallic Chemistry 602 (2000) 97–104
103
Table 2
Table 4
,
,
Bond lengths (A) and angles (°) for 2
Bond lengths (A) and angles (°) for 9
Bond lengths
Bond lengths
MnꢁC(3)
MnꢁC(2)
MnꢁP(1)
P(1)ꢁC(4)
O(1)ꢁC(1)
O(3)ꢁC(3)
O(5)ꢁN
1.789(3)
1.834(3)
2.322(1)
1.837(3)
1.136(3)
1.153(3)
1.231(3)
1.533(4)
MnꢁC(1)
MnꢁO(4)
MnꢁP(2)
P(2)ꢁC(5)
O(2)ꢁC(2)
O(4)ꢁN
1.820(3)
2.050(2)
2.324(1)
1.829(3)
1.147(3)
1.300(3)
1.241(3)
MnꢁC(3)
MnꢁC(2)
MnꢁP(1)
P(1)ꢁC(19)
P(1)ꢁC(12)
P(2)ꢁC(25)
O(1)ꢁC(1)
O(3)ꢁC(3)
C(4)ꢁC(5)
1.808(5)
1.845(5)
2.332(1)
1.824(5)
1.832(5)
1.834(5)
1.138(6)
1.134(6)
1.449(7)
MnꢁC(1)
MnꢁN
1.836(5)
1.996(4)
2.348(1)
1.832(5)
1.830(5)
1.836(5)
1.138(6)
1.139(6)
MnꢁP(2)
P(1)ꢁC(13)
P(2)ꢁC(31)
P(2)ꢁC(11)
O(2)ꢁC(2)
NꢁC(4)
O(6)ꢁN
C(4)ꢁC(5)
Bond angles
C(3)ꢁMnꢁC(1)
C(1)ꢁMnꢁC(2)
C(1)ꢁMnꢁO(4)
C(3)ꢁMnꢁP(1)
C(2)ꢁMnꢁP(1)
C(3)ꢁMnꢁP(2)
C(2)ꢁMnꢁP(2)
P(1)ꢁMnꢁP(2)
O(5)ꢁNꢁO(4)
O(1)ꢁC(1)ꢁMn
O(3)ꢁC(3)ꢁMn
88.81(12)
92.25(13)
94.52(10)
89.51(9)
91.15(11)
90.68(9)
175.65(11)
84.52(3)
119.8(2)
176.2(2)
177.3(3)
C(3)ꢁMnꢁC(2)
C(3)ꢁMnꢁO(4)
C(2)ꢁMnꢁO(4)
C(1)ꢁMnꢁP(1)
O(4)ꢁMnꢁP(1)
C(1)ꢁMnꢁP(2)
O(4)ꢁMnꢁP(2)
O(5)ꢁNꢁO(6)
O(6)ꢁNꢁO(4)
O(2)ꢁC(2)ꢁMn
89.65(12)
172.89(10)
96.49(10)
176.20(8)
86.78(6)
92.09(8)
82.94(5)
123.3(2)
116.9(2)
176.7(3)
Bond angles
C(3)ꢁMnꢁC(1)
C(1)ꢁMnꢁC(2)
C(1)ꢁMnꢁN
C(3)ꢁMnꢁP(1)
C(2)ꢁMnꢁP(1)
C(3)ꢁMnꢁP(2)
C(2)ꢁMnꢁP(2)
P(1)ꢁMnꢁP(2)
O(1)ꢁC(1)ꢁMn
O(3)ꢁC(3)ꢁMn
89.6(2)
91.7(2)
93.2(2)
86.4(2)
175.7(2)
92.1(2)
91.2(2)
84.60(5)
177.4(5)
178.1(5)
C(3)ꢁMnꢁC(2)
C(3)ꢁMnꢁN
C(2)ꢁMnꢁN
C(1)ꢁMnꢁP(1)
NꢁMnꢁP(1)
C(1)ꢁMnꢁP(2)
NꢁMnꢁP(2)
C(4)ꢁNꢁMn
O(2)ꢁC(2)ꢁMn
NꢁC(4)ꢁC(5)
92.7(2)
175.7(2)
90.5(2)
92.6(2)
90.22(12)
176.6(2)
84.89(12)
176.5(4)
178.4(4)
178.8(5)
Hydrogen bonding interactions for 2
Hydrogen bonding interactions for 9
D···A
DꢁH
H···A Angle
D···A
DꢁH
H···A Angle
O1WꢁH1W···O6 a 2.769(10)
O1WꢁH2W···O5 b 3.126(10)
O1WꢁH2W···O2 b 2.684(9)
C4ꢁH4B···O1W c 3.355(11)
0.91
1.11
1.11
0.99
1.98
2.29
1.87
2.51
144.0(7)
130.5(5)
126.6(5)
142.9(3)
O1WBꢁH1W···F2 a 3.23(4)
1.00
0.95
0.95
2.29
2.50
2.51
156(2)
132(1)
155(1)
C7ꢁH7···O1WA b
C7ꢁH7···O1WB b
3.21(3)
3.39(4)
a Symmetry operators: −x+2, y, −z+3/2.
b x, y, z.
a Symmetry operators: x+1/2, −y+3/2, z+1/2.
b −x+3/2, y−1/2, −z+1/2.
c x, y, z.
of bonding is not uncommon and has been discussed
elsewhere [18]. The benzonitrile group has a MnꢁN
,
distance of 1.996(4) A. The bond angle for C(4)ꢁNꢁMn
is 176.5(4)°, demonstrating a linear linkage as expected.
The distances and angles with regard to the benzonitrile
ligand are similar to those reported previously in the
structure of [Mn(CO)(PhCN)(dmpe)2]BPh4 [19].
Table 3
,
Bond lengths (A) and angles (°) for 7
Bond lengths
Mn(1)ꢁC(3)
Mn(1)ꢁC(2)
Mn(1)ꢁP(2)
P(1)ꢁC(5)
P(1)ꢁC(21)
P(2)ꢁC(33)
O(1)ꢁC(1)
O(3)ꢁC(3)
N(1)ꢁC(7)
1.822(3)
1.849(3)
2.325(1)
1.824(3)
1.831(3)
1.831(3)
1.130(4)
1.132(3)
1.402(4)
Mn(1)ꢁC(1)
Mn(1)ꢁC(4)
Mn(1)ꢁP(1)
P(1)ꢁC(15)
P(2)ꢁC(27)
P(2)ꢁC(6)
O(2)ꢁC(2)
N(1)ꢁC(4)
C(5)ꢁC(6)
1.827(3)
1.916(3)
2.337(1)
1.826(3)
1.817(3)
1.833(3)
1.129(3)
1.154(3)
1.490(5)
4. Supplementary material
Crystallographic data (excluding structure factors)
for the structures reported in this paper have been
deposited with the Cambridge Crystallographic Data
Centre as supplementary publication nos. CCDC
136155–CCDC 136157. Copies of this information may
be obtained free of charge from The Director, CCDC,
12 Union Road, Cambridge CB2 1EZ, UK (Fax: +44-
1223-336033; e-mail: deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk). Structure factors are avail-
able upon request from the authors.
Bond angles
C(3)ꢁMn(1)ꢁC(1)
C(1)ꢁMn(1)ꢁC(2)
C(1)ꢁMn(1)ꢁC(4)
C(3)ꢁMn(1)ꢁP(2)
C(2)ꢁMn(1)ꢁP(2)
C(3)ꢁMn(1)ꢁP(1) 176.99(9)
C(2)ꢁMn(1)ꢁP(1)
P(2)ꢁMn(1)ꢁP(1)
90.90(13)
89.58(13)
91.12(13)
92.26(9)
89.51(9)
C(3)ꢁMn(1)ꢁC(2)
C(3)ꢁMn(1)ꢁC(4)
C(2)ꢁMn(1)ꢁC(4) 176.42(11)
C(1)ꢁMn(1)ꢁP(2) 176.76(9)
C(4)ꢁMn(1)ꢁP(2)
C(1)ꢁMn(1)ꢁP(1)
C(4)ꢁMn(1)ꢁP(1)
C(4)ꢁN(1)ꢁC(7)
93.64(12)
89.85(12)
89.60(8)
92.05(9)
89.46(8)
174.0(3)
87.01(9)
84.80(4)
Acknowledgements
O(1)ꢁC(1)ꢁMn(1) 177.0(3)
O(3)ꢁC(3)ꢁMn(1) 177.3(3)
O(2)ꢁC(2)ꢁMn(1) 178.8(3)
N(1)ꢁC(4)ꢁMn(1) 177.4(2)
SMART 1K CCD data was collected through the Ohio
Crystallographic Consortium, funded by the Ohio

104
T.M. Becker et al. / Journal of Organometallic Chemistry 602 (2000) 97–104
[8] G.M. Sheldrick, SHELXTL version 5.03 was used for the structure
solution and generation of figures and tables, University of
Goettingen, Germany and Siemens Analytical X-ray Instruments,
Inc., Madison, WI. Neutral-atom scattering factors were used as
stored in the SHELXTL version 5.03 structure determination
package.
Board of Regents 1995 Investment Fund (CAP-075)
located at the University of Toledo, Instrumentation
Center in A&S, Toledo, OH 43606. JAKB would like
to thank Dr Alan Pinkerton (Department of Chemistry,
University of Toledo) for the use of the SMART 2K
CCD diffractometer.
,
[9] For 7 and 2, data diffracting out to 0.75 A were used in the
refinements. For 7, 59 reflections were omitted from the refine-
ment due to very negative F2 values or other potential systematic
,
errors. In the case of 9, data diffracting out to 0.8 A were used
References
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