New synthetic routes to some nitrosyl rhenium complexes. Crystal, molecular and electronic structure of [ReCl3(NO)(PPh3)2] and [ReCl2(CO)(NO)(PPh3)2] complexes

Article abstract of DOI:10.1016/S0277-5387(99)00120-5

The reactions of the nitrosyl rhenium(II) complex [ReCl₃(NO)(OPPh₃)(PPh₃)] with triphenylphosphine, NaBH₄ in the presence of PPh₃, and CO in the presence of PPh₃ were examined. The rhenium

Full text of DOI:10.1016/S0277-5387(99)00120-5

Polyhedron 18 (1999) 2313–2320
New synthetic routes to some nitrosyl rhenium complexes. Crystal,
molecular and electronic structure of [ReCl3(NO)(PPh3)2] and
[ReCl2(CO)(NO)(PPh3)2] complexes
a
b,1
b
b
c
T.J. Bartczaka , , W. Czurak , J.O. Dzie¸gielewski , B. Machura , A. Jankowska , J. Kusz ,
*
J. Warczewskic
a
~
´ ´
´ ´
X-Ray Crystallography Laboratory, Institute of General and Ecological Chemistry, Technical University of L«odz, 116 Zeromski St., 90-924 L«odz,
Poland
bDepartment of Inorganic and Radiation Chemistry, Institute of Chemistry, University of Silesia, 9 Szkolna St., 40-006 Katowice, Poland
cInstitute of Physics, University of Silesia, 4 Uniwersytecka St., 40-006 Katowice, Poland
Received 10 December 1998; accepted 21 April 1999
Abstract
The reactions of the nitrosyl rhenium(II) complex [ReCl3(NO)(OPPh3)(PPh3)] with triphenylphosphine, NaBH4 in the presence of
PPh3, and CO in the presence of PPh3 were examined. The rhenium nitrosyl complexes [ReCl3(NO)(PPh3)2] (1),
[ReCl2(CO)(NO)(PPh3)2] (2) and [ReH2(NO)(PPh3)3]?1/2C6H6 (3) obtained were characterised by IR, UV–Vis, NMR (1H and 31P)
and magnetochemical measurements. For 1 and 2, the electronic, crystal and molecular structures were determined.
1999 Elsevier
Science Ltd. All rights reserved.
Keywords: Rhenium; Nitrosyl; X-ray structure; Electronic structure; Nitric oxide
1. Introduction
structure, but for the others, we presented both electronic
and molecular structures.
For many years, much attention has been focused on the
synthesis and study of a variety of nitrosyl transition metal
complexes, due to their catalytic abilities and uses in the
production of organonitrogen compounds or in pollutant
control [1–36].
In our recent publications, we disclosed very convenient
single stage syntheses of some nitrosyl rhenium complexes
with phosphine ligands: [ReX2(NO)2(PPh3)2] (X5Cl or
Here, we describe new synthetic methods for
[ReCl3(NO)(PPh3)2] (1), [ReCl2(CO)(NO)(PPh3)2] (2)
and [ReH2(NO)(PPh3)3]?1/2C6H6 (3), their spectroscopic
characterisation, and determination of the electronic, crys-
tal, molecular structures of 1 and 2. We have observed the
formation of the complexes 1, 2 and 3 in the reaction of
[ReCl3(NO)(OPPh3)(PPh3)] with triphenylphosphine, with
CO in the presence of PPh3 and with NaBH4 in the
presence of PPh3, respectively. The complexes 1–3 are
known as rhenium nitrosyl compounds: they have been
obtained by various methods so far. Complex 3 is one of
the most studied rhenium compounds and is a very useful
starting material for the syntheses of a variety of rhenium
nitrosyls [42–45]. We used it to test our new preparative
method. Its crystal and molecular structure were presented
in Ref. [46]. The nitrosyl complex 1 was a product of the
following reactions: [ReCl2(OMe)(NO)(PPh3)2] with HCl
[47], [NEt4][ReCl5(NO)] with PPh3 [48] and
[ReO(OEt)Cl2(PPh3)2] with NO in the presence of
[NEt4N]Cl [49]. Complex 2 was isolated in the reactions
of [ReCl2(OMe)(NO)(PPh3)2] or [ReCl2(NO)(PPh3)3]
Br)
[37],
[ReBr3(Ph)(NO)(PPh3)]
[38],
[ReBr3(NO)(MeCN)(PPh3)] [39], [ReCl3(NO)(OPPh3)
(PPh3)] [40] and [ReCl3(NO)(OPPh3)2] [41]. They are all
products of reductive nitrosylation of oxotrihalogenobis-
(triphenylphosphine)rhenium(V) by gaseous nitric oxide.
For
the
unstable
dinitrosyl
complexes
[ReX2(NO)2(PPh3)2], we determined only their electronic
*Corresponding author. Tel.: 148-42-631-3137; fax: 148-42-631-
3103.
E-mail address: tadekbar@cl-sg.p.lodz.pl (T.J. Bartczak)
1Corresponding author. This author is also a Senior author.
0277-5387/99/$ – see front matter
PII: S0277-5387(99)00120-5
1999 Elsevier Science Ltd. All rights reserved.

2314
T.J. Bartczak et al. / Polyhedron 18 (1999) 2313–2320
with CO [47,50]. However, the crystal, molecular and
electronic structures of 1 and 2 were determined for the
first time in this study.
The synthesis methods given in the literature involve a
multi-stage process; for [ReCl3(NO)(PPh3)2]:
2NaHSO4 1Fe2(SO4)3 12H2O, was purified by passing it
through the washers with concentrated KOH solution and
over solid NaOH. Gaseous CO, obtained from HCOOH,
was purified by passing it through the washers with 50%
KOH and alkaline Na2S2O4 solutions and over solid KOH
and CaCl2.
Solvents were dried and deoxygenated in the usual way
prior to use. The reaction, all preparations and the re-
crystallisation were performed under an argon atmosphere.
[ReOCl3(PPh3)2]9→6%[ReCl2(N2COPh)(PPh3)2]8→6%
[ReCl2(OMe)(NO)(PPh3)2]7→1%[ReCl3(NO)(PPh3)2] [47]
or
[ReOCl3(PPh3)2]8→9%[ReO(OEt)Cl2(PPh3)2]2→5%
(NMe4)2[Re(NO)Cl5]6→0%[ReCl3(NO)(PPh3)2] [10,45,57]
Our method is as follows:
2.1. Preparation of [ReCl3(NO)(PPh3 )2 ]
The solution of [ReCl3(NO)(OPPh3)(PPh3)] (0.4 g,
0.46 mmol) and PPh3 (0.4 g, 1.5 mmol) in CH2Cl2
(30cm3) was refluxed for 2 h. The colour immediately
changed from green to dark red. The dark red precipitate
was formed by an addition of 100 cm3 of EtOH and
filtered off after 20 min. The product was washed with
cold ether and dried in vacuo. Yield: 0.37 g (0.44 mmol)
[ReCl3(NO)(PPh3)2].
[ReOCl3(PPh3)2]5→1%[ReCl3(NO)(OPPh3)(PPh3)]9→5%
[ReCl3(NO)(PPh3)2]
In the case of [ReCl2(NO)(CO)(PPh3)2], the methods
presented in the literature are:
[ReOCl3(PPh3)2]9→6%[ReCl2(N2COPh)(PPh3)2]8→6%
[ReCl2(OMe)(NO)(PPh3)2]5→5%[ReCl2(NO)(CO)(PPh3)2
Crystals suitable for X-ray structure determination were
obtained by slow evaporation of an acetonitrile solution of
nitrosyl rhenium(II) complex at room temperature.
2.2. Preparation of [ReCl2(CO)(NO)(PPh3 )2 ]
[47]
or
(A) CO was passed through a vigorously stirred and
refluxing solution of [ReCl3(NO)(OPPh3)(PPh3)] (0.3 g,
0.35 mmol) and PPh3 (0.3 g, 1.1 mmol) in tetrahydrofuran
(THF; 50 cm3). The reaction was carried out for 6–7 h.
The colour changed first from green to dark red and then
gradually to yellow. The resulting solution was evaporated
to a volume of 10 cm3. The bright yellow precipitate was
formed by the addition of 100 cm3 of EtOH and, after 20
min, it was filtered off. The product was washed with cold
ether and dried in vacuo. Yield: 0.22 g (0.27 mmol)
[ReCl2(CO)(NO)(PPh3)2]. When the reaction was carried
out in the absence of triphenylphosphine, the yields of
[ReCl2(CO)(NO)(PPh3)2] dropped to 5% (0.014 g). Crys-
tals suitable for X-ray structure determination were ob-
tained by slow evaporation of an acetonitrile solution of
nitrosyl rhenium(I) complex at room temperature.
(B) CO was passed through a vigorously stirred and
refluxing solution of [ReCl3(NO)(PPh3)2] (0.3 g, 0.35
mmol) in THF (50 cm3). The reaction was carried out for
6–7 h. The colour changed gradually from dark red to
yellow. The resulting solution was evaporated to a volume
of 10 cm3. A light yellow precipitate was formed on the
addition of 100 cm3 of EtOH and, after 20 min, it was
filtered off. The product was washed with cold ether and
[ReOCl3(PPh3)2]9→6%[ReCl2(N2COPh)(PPh3)2]8→6%
[ReCl2(OMe)(NO)(PPh3)2]9→1%[ReH2(NO)(PPh3)3]9→5%
[ReCl2(NO)(PPh3)3]9→7%[ReCl2(NO)(CO)(PPh3)2] [42]
Our method is as follows:
[ReOCl3(PPh3)2]5→1%[ReCl3(NO)(OPPh3)(PPh3)]7→6%
[ReCl2(NO)(CO)(PPh3)2]
Our two-staged preparative procedures have comparable
yields to those of the methods described in the literature.
Therefore, the aim of our work was to simplify the
synthesis of an important group of rhenium compounds, to
determine their crystal and electronic structures, and also
to characterise their magnetic and spectroscopic properties
in the range of electron, infrared and 31P NMR spec-
troscopies.
2. Experimental
Triphenylphosphine and NH4ReO4 were purchased from
Aldrich Chemical Co. and used without further purifica-
tion.
dried in vacuo. Yield: 0.23
[ReCl2(CO)(NO)(PPh3)2].
g
(0.28 mmol)
The [ReOCl3(PPh3)2] and [ReCl3(NO)(OPPh3)(PPh3)]
complexes were synthesised according to methods de-
scribed in the literature [40,51]. Gaseous NO, obtained in
2.3. Preparation of [ReH2(NO)(PPh3 )3 ]?1/2C6H6
the
reaction:
2NaNO2 13H2SO4 12FeSO4 →2NO1
A solution of [ReCl3(NO)(OPPh3)(PPh3)] (0.15 g, 0.17

T.J. Bartczak et al. / Polyhedron 18 (1999) 2313–2320
2315
mmol), PPh3 (0.15 g, 0.57 mmol) and NaBH4 (0.04 g, 0.1
mmol) in ethanol (30 cm3) was refluxed for 2 h. The
colour immediately changed from green to yellow. The
yellow precipitate was filtered off. The crude product was
solved in CH2Cl2. NaCl, which is insoluble in CH2Cl2,
was filtered off and the precipitate of [ReH2(NO)(PPh3)3]
was formed on addition of 100 cm3 of EtOH. The
diamagnetic complex was recrystallised from a mixture of
1H and 31P NMR were obtained at room temperature in
CDCl3 solution using a Varian VXR300 spectrometer. The
sample solutions were prepared using monocrystals of the
complex. In the case of the proton resonance, tetra-
methylsilane (TMS) was used as an internal standard, and
for phosphorus resonance, an 85% H3PO4 aqueous solu-
tion was used.
Magnetic susceptibilities were measured at 296 K by the
Faraday method.
ethanol and benzene. Yield: 0.16
g (0.15 mmol)
[ReH2(NO)(PPh3)3]?1/2 C6H6. Anal. calcd.: C, 65.5; H,
4.82; N, 1.34. Found: C, 64.9; H, 4.4; N, 1.31. Infrared
spectrum: 1965 cm21 (nRe–H), 1794 cm21(nRe–H), 1630
cm21 (nN–O). 31P NMR (CDCl3): two singlets at 18.38 and
2.5. Crystal structure determination and refinement
1
27.97 ppm. H NMR (CDCl3): two quartets at 1.32 and
All of the three-dimensional X-ray intensity data were
collected on a Kuma KM-4 diffractometer with graphite
monochromated Mo–Ka radiation (l50.71073 A) at
2.54 ppm (JPH 530 Hz, JHH 56 Hz); phenyl multiplets
were found between 6.9 and 7.24 ppm). UV–Vis spec-
troscopy: 29 670 cm21 (´52432 dm3 mol21 cm21),
37 040 cm21 (´516 768 dm3 mol21 cm21), 45 455 cm21
(´518 175 dm3 mol21 cm21).
˚
room temperature. Details concerning crystal data and
refinement for 1 and 2 are given in Table 1. Lorentz,
polarisation and empirical absorption corrections were
applied for 1 and 2. The structures of the complexes were
solved by means of the Patterson and Fourier methods. All
of the non-hydrogen atoms were refined anisotropically
using the full-matrix, least-squares technique. The posi-
tions of the hydrogen atoms of the phenyl rings were found
from subsequent difference Fourier syntheses and were
treated as ‘riding’ on the adjacent carbon atom [d(C–H)5
2.4. Physical measurements
Infrared spectra were recorded on a Nicolet Magna 560
spectrophotometer in the spectral range 4000–400 cm21
,
with the samples in the form of potassium bromide pellets.
Electronic spectra were measured on a Beckman 5240
spectrophotometer in the range 800–220 nm in deoxy-
genated dichloromethane solution.
˚
0.96 A] and refined with an individual isotropic tempera-
ture factor that was equal to 1.2 times the value of the
Table 1
Crystal data and structure refinement for 1 and 2
1
2
Empirical formula
Formula weight
Temperature, K
C36H30Cl3NOP2Re
847.10
293(2)
0.71073
C37H30Cl2NO2P2Re
827.70
293(2)
˚
Wavelength, A
0.71073
Crystal system
Space group
Unit cell dimensions, A
Monoclinic
C2/c
Monoclinic
C2/c
˚
a525.553(9)
b59.563(4)
c515.890(6)
b5116.9(3)8
3327(2)
a524.494(4)
b59.500(2)
c515.963(3)
b5116.030(10)8
3337(11)
4
1.742
4.01
1724
3
˚
Volume, A
Z
4
Density (calculated), Mg/m3
Absorption coefficient, mm21
F(000)
1.691
4.02
1668
Crystal size, mm
u range for data collection
Index ranges
0.3130.2130.13
2.31 to 25.058
226#h#29; 21#k#11;
218#l#1
0.0830.0930.20
2.34 to 25.058
229#h#18; 0#k#11;
219#l#18
Reflections collected
3693
3033
Independent reflections
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I.2s(I)]
R indices (all data)
2944 (Rint 50.0285)
Full-matrix least-squares on F2
2925/0/202
2949 (Rint 50.0214)
Full-matrix least-squares on F2
2943/0/215
1.06
1.18
R150.033, wR250.087
R150.028, wR250.058
R150.055, wR250.101
R150.040, wR250.067
23
23
˚
˚
Largest diff. peak and hole
4.54 and 21.21 eA
1.50 and 20.73 eA

2316
T.J. Bartczak et al. / Polyhedron 18 (1999) 2313–2320
equivalent temperature factor of the parent carbon atom.
SHELXL97 [52] and SHELXTL [53] programs were used
for all of the calculations. Atomic scattering factors were
those incorporated in the computer programs.
3. Results and discussion
The [ReCl3(NO)(OPPh3)(PPh3)] complex reacts with
CO to give [ReCl2(CO)(NO)(PPh3)2], but its yield in this
synthesis is extremely low (see Section 2). When the
reaction of [ReCl3(NO)(OPPh3)(PPh3)] with CO is carried
out in the presence of triphenylphosphine, the yields of the
nitrosyl rhenium (1) complex increase considerably. The
first step in the reaction of [ReCl3(NO)(OPPh3)(PPh3)]
with CO, carried out in the presence of PPh3, involves
replacement of the triphenylphosphine oxide molecule by
PPh3 to generate 1. Complex 1 is then reduced by CO to 2.
In order to confirm this mechanism, we also carried out the
reaction of the [ReCl3(NO)(OPPh3)(PPh3)] complex with
only PPh3. Then, the product of this reaction, complex 1,
was treated with CO. In this case, nitrosyl complex 2 was
isolated also.
Fig. 1. The molecular structure of 1.
180.08, and the bond lengths discussed above confirm the
linear co-ordination of the nitrosyl ligand. The Cl(2) ligand
is trans to the nitrosyl group (p-acceptor ligand) and this
The [ReCl3(NO)(OPPh3)(PPh3)] reacts with NaBH4 in
the presence of PPh3 to yield [ReH2(NO)(PPh3)3]?
1/2C6H6.
˚
is why the bond Re(1)–Cl(2)52.398(2) A is slightly
˚
longer than Re(1)–Cl(1)52.378(2) A.
3.1. Molecular structure of
trichloronitrosylbis(triphenylphosphine)rhenium(II)
3.2. Molecular structure of
dichloro(carbonyl)(nitrosyl)bis(triphenylphosphine)
rhenium(I)
A similar structure of [ReCl3(NO)(PMePh2)2] was
published previously [58]. However, the compound crys-
tallised in the different crystal system (triclinic), no bond
lengths and angles were given and the R factor for 4118
diffractometer data was 0.10.
The numbering scheme of 1 is shown in Fig. 1. The
Re(1) atom is octahedrally surrounded by three chlorine
atoms: Cl(1), Cl2) and Cl(1a), a nitrosyl group, N(1)–
O(1), and two phosphorus atoms, P(1) and P(1a). The
central ion, Re(1), the nitrosyl group, N(1)–O(1), and one
of the chloride ligands, Cl(2), occupy special positions;
they all lie on two-fold axis. In the [ReCl3(NO)(PPh3)2]
complex, in contrast to the starting material
[ReCl3(NO)(OPPh3)(PPh3)], the phosphine ligands are in
a trans arrangement.
The numbering scheme of 2 is shown in Fig. 2. The
Re(1) atom is octahedrally surrounded by two chlorine
atoms, Cl(1), Cl(2), a nitrosyl group, N(1)–O(1), a
carbonyl group, C(37)–O(2), and two phosphorus atoms,
P(1) and P(1a). The central ion, Re(1), the nitrosyl group,
Table 2
˚
Selected bond lengths (A) and angles (8) for 1
Bond lengths
Angles
Re(1)–N(1)
Re(1)–Cl(1)
Re(1)–Cl(2)
Re(1)–P(1)
P(1)–C(1)
P(1)–C(7)
P(1)–C(13)
N(1)–O(1)
1.765(9)
2.378(2)
2.398(2)
2.530(2)
1.819(6)
1.822(6)
1.826(6)
1.200(11)
N(1)–Re(1)–Cl(1)
N(1)–Re(1)–Cl(2)
Cl(1)–Re(1)–Cl(2)
N(1)–Re(1)–P(1)
Cl(1)–Re(1)–P(1)
Cl(2)–Re(1)–P(1)
C(1)–P(1)–C(7)
C(1)–P(1)–C(13)
C(7)–P(1)–C(13)
C(1)–P(1)–Re(1)
C(7)–P(1)–Re(1)
C(13)–P(1)–Re(1)
O(1)–N(1)–Re(1)
90.43(4)
180
89.57(4)
90.60(4)
92.51(6)
89.40(4)
106.7(3)
105.5(3)
100.8(3)
107.0(2)
119.1(2)
116.8(2)
180
The most important bond lengths and angles for 1 are
reported in Table 2. The Re–NO bond distance of 1.765(9)
˚
A is in good agreement with values previously found by
˚
A
others,
for
example,
1.76(2)
in
in
in
˚
[ReF(CO)(NO)(PPh3)3][BF4] [50], 1.749(11)
A
˚
(NEt4)[Re(NO)Cl4(py)]
[54]
and
1.77
A
[ReH2(NO)(PPh3)3]?1/2 C6H6 [46]. The N(1)–O(1) bond
˚
˚
length of 1.200(11) A is in the range 1.10–1.25 A, which
is expected for NO1 [1]. The value of Re–N–O angle,

T.J. Bartczak et al. / Polyhedron 18 (1999) 2313–2320
2317
N(1)–O(1), and one of the chloride ligands, Cl(1), occupy
special positions as they all lie on a two-fold axis [59].
Therefore, the C(37)–O(2) group and Cl(2) are disordered
and were treated during refinement with site occupation
factors equal to 0.5. This affected the accuracy of the
associated bond lengths and angles. ESDs of the bonds
˚
involved in the disorder are, on average, 0.05 A, compared
˚
to 0.001–0.002 A for the bonds of Re(1) with other atoms.
The most important bond lengths and angles for 2 are
reported in Table 3. The value of the Re(1)–N(1)–O(1)
angle, 180.08, and the bond lengths for Re(1)–N(1),
˚
˚
1.829(6) A, and N(1)–O(1), 1.157(8) A, confirm the linear
co-ordination of the nitrosyl ligand.
3.3. Spectroscopic characterisation of the
[ReCl3(NO)(PPh3 )2 ] complex
The trans geometry of phosphine ligands in 1 was
clearly established by 31P NMR spectroscopy. The 31P
NMR spectrum of 1 consists of one singlet at 29.65 ppm.
Fig. 2. The molecular structure of 2.
1
The H NMR spectrum of 1 shows only phenyl multi-
plets between 7.44 and 7.87 ppm.
Table 3
Selected bond lengths (A) and angles (8) for 2
A strong band, corresponding to the stretching vibration
of the nitrosyl group, appears at 1734 cm21. Table 4
contains the assignments of characteristic bands in the IR
range for 1 [55].
[ReCl3(NO)(PPh3)2] is a paramagnetic compound with
a magnetic moment equal to 1.8 BM, corresponding to one
unpaired electron.
The positions and molar absorption coefficients of
electronic bands for 1 and the electronic transitions as-
signed to the bands are shown in Table 5. The first two
absorption bands in the electronic spectrum of 1 corre-
spond to the electron transitions between d orbitals split in
a ligand field of C2v symmetry. The band at 26 180 cm21
˚
Bond lengths
Angles
Re(1)–N(1)
Re(1)–C(37)
Re(1)–Cl(1)
Re(1)–Cl(2)
Re(1)–P(1)
C(37)–O(2)
N(1)–O(1)
P(1)–C(1)
1.829(6)
1.93(2)
2.428(2)
2.410(6)
2.492 (1)
1.16(2)
1.157(8)
1.822(5)
1.831(5)
1.826(5)
N(1)–Re(1)–C(37)
N(1)–Re(1)–Cl(2)
N(1)–Re(1)–Cl(1)
C(37)–Re(1)–Cl(1)
Cl(2)–Re(1)–Cl(1)
N(1)–Re(1) –P(1)
C(37)–Re(1)–P(1)
Cl(2)–Re(1)–P(1)
Cl(1)–Re(1)–P(1)
C(1)–P(1)–C(7)
86.8(9)
88.4(1)
180
93.2(9)
91.6(1)
90.62(3)
92.5(8)
92.3(2)
89.4(3)
105.5(2)
101.3(2)
104.9(2)
118.8(2)
108.3(1)
116.8(2)
168.0(3)
180
P(1)–C(13)
P(1)–C(7)
C(1)–P(1)–C(13)
C(13)–P(1)–C(7)
C(1)–P(1)–Re(1)
C(7)–P(1)–Re(1)
C(13)–P(1)–Re(1)
O(2)–C(37)–Re(1)
O(1)–N(1)–Re(1)
is a result of two transitions: dxy →p*NO and dxy →dx
.
2
2
–y
The band at 36 360 cm21 is a charge transfer transition as
it corresponds to transition of pbRe–Cl electrons to the
suitable d orbitals of rhenium. The band of the highest
energy is a result of an electronic transition in the
Table 4
Infrared spectral data for 1 and 2
Band position (cm21
)
Assignment
[ReCl3(NO)(PPh3)2]
[ReCl2(CO)(NO)(PPh3)2]
1990
n(CO)
1734
1722
n(NO)
1431
1433
n(P–C6H5)
1482
1093
750 and 725
690
534
1479
1093 and 1026
746
694
524
d(C–CH in the plane)
d(C–H in the plane)
d(C–C out of the plane)
d(C–C in the plane)
n(Re–N)

2318
T.J. Bartczak et al. / Polyhedron 18 (1999) 2313–2320
Table 5
Band positions, molar absorption coefficients and assignments for 1 and 2
[ReCl3(NO)(PPh3)2]
[ReCl2(CO)(NO)(PPh3)2]
Band position
Band positions
(cm21
Molar absorption
coefficients
Assignments
Molar absorption
coefficient
Assignment
)
(cm21
)
(dm3 mol21 cm21
)
(dm3 mol21 cm21
)
15 040
34
dxy →dyz
14 700
10
dyz →dx
dyz →p*NO
dxy →dxz
dxy →dx
dyz →dz
2
2
y
–
a
18 760
26 180
2800
3920
dxy →dxz
dxy →p*NO
dxy →dx
15 385
36 365
13
7360
2
2
–y
2
2
2
–y
dxy →p*NO
dxy →p*CO
36 360
41 220
16 858
17 220
pbRe–Cl →dyz
pCb
38 460
41 670
16 453
18 123
dyz →dz
2
→3dfosfor
5
pbC6H5 →3dfosfor
H
6
a Transition forbidden because of symmetry.
phosphine ligand molecule. Based on the data in Table 5,
the values of the ligand field parameters Dq, Ds and Dt
have been defined and the energies of molecular orbitals
for 1 have been estimated. The values of ligand field
parameters are shown in Table 6; Fig. 3 presents a
simplified molecular orbital (MO) diagram for complex 1.
A relatively high p*NO energy level has also been
defined by other authors [56].
In the nitrosyl complex, the Re ion is present in the 12
oxidation state, and its electronic configuration, consider-
ing splitting of d orbitals in C2v symmetry, is as follows:
(dxy)2(dyz)2(dxz)1.
because of symmetry. This fact explains why the intensity
of the band is so low. The next absorption band in the
electronic spectrum of 2 corresponds to the electron
transitions between d orbitals split in a ligand field of C2
symmetry. Its intensity is typical for d–d transitions. The
relatively high intensity of the bands at 36 365 and 38 460
cm21 results from a partial contribution of the transitions
dxy →p*NO and dxy →p*CO, respectively. The band of the
highest energy is a result of an electronic transition in the
phosphine ligand molecule. Based on the data of Table 5,
the values of the ligand field parameters, Dq, Ds and Dt,
have been defined and the energies of molecular orbitals
for 2 have been estimated. The values of the ligand field
parameters are shown in Table 6; Fig. 4 presents a
simplified MO diagram for 2.
3.4. Spectroscopic characterisation of the
[ReCl2(CO)(NO)(PPh3 )2 ] complex
In the nitrosyl complex, the Re ion is present in a 11
oxidation state, and its electronic configuration, consider-
ing splitting of d orbitals in C2 symmetry, is as follows
(dxy)2(dxz)2(dyz)2.
Table 4 contains the assignments of characteristic bands
in the IR range for 2 [55]. Strong bands corresponding to
the stretching vibrations of nitrosyl and carbonyl groups
appear at 1722 and 1990 cm21, respectively.
[ReCl2(CO)(NO)(PPh3)2] is a diamagnetic compound.
The positions and molar absorption coefficients of
electronic bands for 2 and the electronic transitions as-
signed to the bands are shown in Table 5. Transition of dyz
electrons to p*NO, which is partially responsible for the
origination of the smallest energy band, is forbidden
4. Conclusion
In the light of the results presented above, the simplified
synthesis of the rhenium compounds examined has a
distinct advantage in comparison to previously used pre-
Table 6
Values of ligand field parameters for 1 and 2
Ligand field parameter
Value (cm21
)
[ReCl3(NO)(PPh3)2]
[ReCl2(CO)(NO)(PPh3)2]
Dq
Ds
Dt
2617
25537
430
3636
25282
293

T.J. Bartczak et al. / Polyhedron 18 (1999) 2313–2320
2319
Fig. 3. Molecular orbitals diagram for 1.
Fig. 4. Molecular orbitals diagram for 2.
parative methods. It is less labour- and material-consuming
and it provides a purer product with a comparable yield.
The presented results also allowed for the determination of
the
crystal
and
electronic
structures
of
[ReCl3(NO)(PPh3)2] and [ReCl2(CO)(NO)(PPh3)2], and
their spectroscopic characteristics.

2320
T.J. Bartczak et al. / Polyhedron 18 (1999) 2313–2320
[28] T. Beringhelli, G. Ciani, G. D’Alfonso, H. Molinari, A. Sironi, M.
Supplementary data
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This work was supported financially by the Polish State
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