Rhenium(V) complexes with tridentate P,N,S ligands

Article abstract of DOI:10.1016/j.poly.2011.11.023

Novel, potentially tridentate ligands with P,N,S donor sets (HL ^diethyl and HL^morph) were prepared from reactions of N-(dialkyl)thiocarbamoylbenzimide chlorides with 2-(diphenylphosphinomethyl) aniline. They readily react with (NBu

Full text of DOI:10.1016/j.poly.2011.11.023

Polyhedron 33 (2012) 218–222
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Polyhedron
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Rhenium(V) complexes with tridentate P,N,S ligands
⇑
Jennifer Schroer, Ulrich Abram
Freie Universität Berlin, Institute of Chemistry and Biochemistry, Fabeckstr. 34-36, D-14195 Berlin, Germany
a r t i c l e i n f o
a b s t r a c t
Novel, potentially tridentate ligands with P,N,S donor sets (HLdiethyl and HLmorph) were prepared from
reactions of N-(dialkyl)thiocarbamoylbenzimide chlorides with 2-(diphenylphosphinomethyl)aniline.
They readily react with (NBu4)[ReOCl4] under formation of air-stable [ReOCl2(LR)] complexes, in which
the tridentate ligands coordinate meridionally. A similar coordination mode is observed in the nitridorhe-
nium(V) complex [ReN(OReO3)(PPh3)(Ldiethyl)], which can be obtained from a reaction of [ReNCl2(PPh3)2]
and HLdiethyl. The complexes were characterized spectroscopically and by X-ray structure analyses.
Ó 2011 Elsevier Ltd. All rights reserved.
Article history:
Received 15 October 2011
Accepted 16 November 2011
Available online 25 November 2011
Keywords:
Rhenium
Oxo complexes
Nitrido complexes
Tridentate ligands
Structure analysis
1. Introduction
ligands up to four, so that nowadays N-(dialkyl)thiocarbamoyl-
benzamidines with S,N,N, S,N,O, S,N,S and S,N,N,S donor sets are
Tri-, tetra- or multiple-dentate ligands, which form stable or
kinetically inert complexes with rhenium and technetium are still
of interest for nuclear medical labeling procedures, since previous
studies have shown that mono- and bidentate ligand systems may
suffer from insufficient in vivo stability due to rapid ligand ex-
change reactions with plasma components [1–5]. For common
technetium(V) and rhenium(V) cores, ligands with ‘medium’ and
‘soft’ donor atoms are recommended [1,2]. Thus, chelators with a
mixed phosphorus, sulfur and nitrogen donor sphere should be
very suitable. However, there is surprisingly less known about rhe-
nium or technetium complexes with such ligands. One example
has been extensively studied. It is a thiolato-substituted amide,
which has been prepared by a reaction of N-[2-(diphenylphospha-
nyl)]benzoyloxylsuccinimide with S-(triphenylmethyl)-2-amino-
ethanethiol [6,7]. A more facile synthesis of P,N,S ligands is
possible following a general procedure, which has been applied
to various ligands including amino acid derivatives: reactions be-
tween N-(dialkyl)thiocarbamoylbenzimidoyl chlorides with substi-
tuted amines [8–13].
available (Scheme 1), and their coordination chemistry with rhe-
nium and is under study [8–13,17]. These compounds are known
for a high flexibility in their donor functions and peripheral sub-
stituents as well as the formation of stable chelates with a number
of metal ions.
As part of our systematic work in the synthesis of phosphine-
containing ligands for rhenium and technetium, we report in the
present work about reactions of 2-(diphenylphosphinomethyl)ani-
line with N-(dialkyl)thiocarbamoylbenzimidoyl chlorides, which
yield potentially tridentate P,N,S ligands. Furthermore, we report
about their coordination behavior towards oxorhenium(V) and
nitridorhenium(V) centers.
2. Results and discussion
Reactions of 2-(diphenylphosphinomethyl)aniline with substi-
tuted thiocarbamoylbenzimidoyl chlorides in tetrahydrofurane
(Eq. (1)) give the tridentate ligands in good yields. Small amount
(approximately 5%) of impurities due the formation of the corre-
sponding phosphine oxides are formed during these reactions.
They can be removed by subsequent recrystallization under anaer-
obic conditions in order to obtain the pure products. For complex
formation with Re(V) compounds, however, the crude products
can be used without purification, since the impurities have no
influence on the desired complex formation and potential side-
products such as phosphine oxide complexes do not play a role
as long as a slight excess of the ligands is applied.
Since the first syntheses of N-(dialkyl)thiocarbamoylbenzimi-
doyl chlorides and their reaction products with primary amines,
N-(dialkyl)thiocarbamoylbenzamidines [14,15], a large number of
different transition metal complexes with such ligands were syn-
thesized and extensively studied [16]. For a long time, however,
this ligand system was restricted to bidentate ligands (S,N type li-
gands of Scheme 1). Recently, we extended the denticity of these
⇑
The 31P{1H} NMR spectra of HLdiethyl and HLmorph reveal each
one singlet at À17.3 ppm (HLdiethyl) and À16.9 ppm (HLmorph).
Corresponding author. Tel.: +49 30 838 54002; fax: +49 30 838 52676.
E-mail address: ulrich.abram@fu-berlin.de (U. Abram).
0277-5387/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2011.11.023

J. Schroer, U. Abram / Polyhedron 33 (2012) 218–222
219
NR1R2
N
Ph
NR1R2
N
Ph
NH2
NR1R2
N
Ph
S
HN
HO
S
HN
S
N
S,N,N
S,N
S,N,O
H
NR1R2
N
Ph
Ph
N
NH HN
S
N
S
N
NH
NR3R4
S
S
NR1R2
NR1R2
S,N,S
S,N,N,S
Scheme 1.
1H NMR spectra indicate hindered rotation around the C–N(alkyl)
bonds, which can clearly be seen from the splitting patterns of
the methylene and methyl signals of the morpholine and diethyl
substituents. This is a common feature of the NMR spectra of this
type of ligands and analogous coupling patterns were already de-
scribed for similar thiocarbamoylbenzamidines. The IR spectra
clearly show the vibration of the NH bonds at 3337 cmÀ1 (HLmorph
)
and 3325 cmÀ1 (HLdiethyl). Broad bands for the CN bonds are found
at 1628 cmÀ1 (HLmorph) and 1612 cmÀ1 (HLdiethyl).
Reactions of HLR with (NBu4)[ReOCl4] result in green precipi-
tates or crystals. The products have the composition [ReOCl2(LR)]
(Eq. (2)). The organic ligand is single deprotonated and coordinates
meridionally tridentate in the equatorial coordination sphere of
rhenium via the phosphorus, nitrogen and sulfur donor atoms.
The remaining two positions are occupied by chlorido ligands.
The 31P{1H} NMR spectra of both compounds each show a sin-
glet. The signals appear at 5.7 ppm for [ReOCl2(Ldiethyl)] and at
7.1 ppm for [ReOCl2(Lmorph)]. This indicates a low-field shift of
more than 20 ppm with respect to the signals observed in the spec-
tra of the non-coordinated ligands, and confirms the presence of
only one phosphorus atom in the complexes. The 1H NMR spectra
of both compounds are complex, which is due to hindered rotation
around the C–NR1R2 bonds as has already been described for the
uncoordinated benzamidines HLdiethyl and HLmorph. This feature is
also common for metal complexes with thiocarbamoylbenzami-
dines and leads to a splitting of the signals of the alkyl groups of
the diethyl and morpholine substituents. Two multiplets can be as-
signed to the two methyl groups at 1.38 ppm in the case of
(Ldiethyl)À, whereas the two methylene groups in this ligand are
splitted into four signals at 3.58, 3.81, 4.49 and 4.99 ppm. In case
of (Lmorph)À, five multiplets at 3.80, 4.21, 4.39, 4.75 and 5.20 ppm
can be assigned to the methylene groups of the morpholine substi-
tuent. The methylene protons adjacent to the phosphorus atoms
produce multiplets at 4.28 ppm ([ReOCl2(Ldiethyl)]) and 4.39 ppm
([ReOCl2(Lmorph)], respectively. The latter one overlaps with a sig-
nal of one of the methylene groups of the morpholine substituent.
The IR spectra of both complexes confirm the deprotonation of
Fig. 1. Ellipsoid representation [31] of the molecular structure of (a)
[ReO-Cl2-(Ldiethyl)] and (b) [ReOCl2(Lmorph)]. Thermal ellipsoids represent 50%
probability. H atoms have been omitted for clarity.
Table 1
Selected bond lengths (Å) and angles (°) in [ReOCl2(Ldiethyl)] and [ReOCl2(Lmorph)].
[ReOCl2(Ldiethyl)]
[ReOCl2(Lmorph)]
Re1–O10
Re1–C11
Re1–C12
Re1–S1
Re1–N5
Rel–P1
C2–N3
C2–N51
N3–C4
C4–N5
1.685(4)
2.401(2)
2.466(2)
2.344(2)
2.084(5)
2.461(2)
1.328(8)
1.330(7)
1.316(7)
1.356(7)
1.424(7)
169.4(7)
163.80(5)
163.3(2)
87.92(5)
1.671(6)
2.399(2)
2.482(2)
2.333(2)
2.086(7)
2.452(2)
1.33(2)
1.330(7)
1.32(2)
1.36(2)
N5–C16
1.44(2)
N5–Rel–CH
SI–Rel–PI
O10–Rel–C12
C11–Rel–C12
170.1(2)
164.48(9)
166.8(2)
87.55(9)
the organic ligands by the absence of mNH vibrations. Strong, broad
with one molecule in the asymmetric unit, whereas
[ReOCl2-(Lmorph)] crystallizes in the monoclinic space group P21/c
with one complex molecule and two molecules of solvent acetone
in the asymmetric unit. Ellipsoid representations of the complex
molecules are shown in Fig. 1. Selected bond lengths and angles
for both compounds are given in Table 1.
The trans influence of the oxo ligand lengthens the Re–Cl2
bonds to values of 2.466(2) and 2.482(2) Å, respectively, in com-
parison to approximately 2.40 Å for the Re1–Cl1 bonds in the equa-
torial coordination spheres. Inside the organic ligands, a bond
bands can be assigned to the C@N double bonds of the organic li-
gands in both cases. Both bands, which are found at 1523 cmÀ1
for [ReOCl2(Ldiethyl)] and at 1512 cmÀ1 for [ReOCl2(Lmorph)] are
bathochromically shifted by approximately 100 cmÀ1 with respect
to HLdiethyl and HLmorph. These shifts indicate chelate formation with
a large degree of p-electron delocalization within the chelate rings.
Crystals suitable for X-ray diffraction were obtained by crystal-
lization from a mixture of CH2Cl2/acetone or pure acetone. [Re-
OCl2(Ldiethyl)] crystallizes in the orthorhombic space group Fdd2

220
J. Schroer, U. Abram / Polyhedron 33 (2012) 218–222
Table 2
length equalization of the C2–N3, C2–N51, N3–C4 and C4–N5
bonds is observed. All these bonds show partial double bond char-
acter with bond lengths between 1.32(2) and 1.36(2) Å. By the fact
that the C2–N51 bond is involved in this p-electron delocalization,
the hindered rotation, which is detected in the NMR spectra, can
Selected bond lengths (Å) and angles (°) in [ReN(OReO3)(PPh3)(Ldiethyl)].
Re1–N10
Re1–P1
Re1–N5
Re1–S1
Rel–O1
Re1–P2
1.654(6)
2.448(2)
2.150(5)
2.369(2)
2.348(5)
2.433(2)
S1–C2
1.736(7)
1.33(1)
1.330(9)
1.327(9)
1.321(9)
1.734(5)
Re2–O2
Re2–O3
Re2–O4
N10–Re1–O1
Re1–O1–Re2
P1–Re1–P2
1.708(8)
1.688(9)
1.709(5)
173.4(2)
151.0(3)
96.87(6)
C2–N51
C2–N3
N3–C4
C4–N5
Re2–O1
readily be explained.
With regard to the completely identical reaction patterns of
HLdiethyl and HLmorph with the oxorhenium(V) core, only the reac-
tion of HLdiethyl with the common nitridorhenium(V) precursor
[ReNCl2(PPh3)2] was studied in order to give information about
the products formed with the nitridorhenium(V) core.
double bond character with bond lengths between 1.688(9) and
1.709(5) Å. The Re1–O1–Re2 bond is bent with an angle of
151.0(3)°. This bonding situation is common for perrhenato ligands
[17–23]. In the present case, there was no evidence for the forma-
tion of a square-planar or trigonal-bipyramidal, cationic [Re-
The reaction of HLdiethyl with [ReNCl2(PPh3)2] was performed in
CH2Cl2. The sparingly soluble starting complex rapidly dissolves
after the addition of the phosphinobenzamidine and a supporting
base such as NEt3. An attempted reaction without the supporting
base did not show any formation of a ligand exchange product
within 1 h due to the low solubility of the starting complex. The
product could be isolated as orange-brown crystals after overlayer-
ing the reaction solution with methanol. X-ray crystal structure
determination showed the formation of a nitridorhenium(V) che-
late of the composition [ReN(OReO3)(PPh3)(Ldiethyl)]. An ellipsoid
representation of this complex is depicted in Fig. 2 and selected
bond lengths and angles are listed in Table 2. The coordination
sphere of Re1 can be best described as a distorted octahedron.
The thiocarbamoylbenzamidine coordinates meridionally triden-
tate to the Re(V) center after single deprotonation. The equatorial
coordination plane of the complex is completed by one molecule
triphenylphosphine, whereas the axial positions are occupied by
one nitrido ligand N10 and a perrhenato ligand.
N(PPh3)(Ldiethyl)]+ complex or
a species of the composition
[ReN(PPh3)Cl(Ldiethyl)]. Explicit experiments in order to exchange
the weakly bonded perrhenato ligand have not been undertaken.
The 31P{1H} NMR spectrum of [ReN(OReO3)(PPh3)(Ldiethyl)] re-
veals two signals at 21.6 and 46.0 ppm, which can be assigned to
phosphorus atoms of (Ldiethyl À and PPh3, respectively. The 1H
)
NMR spectrum of the compound is complex as those of the oxorhe-
nium(V) chelates. It shows splittings of the signals of the methy-
lene and methyl protons of the diethyl substituents of the
organic ligand as was discussed for [ReOCl2(Ldiethyl)]. One multiplet
at 4.28 ppm can be assigned to the methylene group next to the
phosphorus atom. Deprotonation and coordination of the amino
group can be concluded from the absence of the NH NMR signal.
The IR spectrum confirms this fact as well by the absence of a
m
NH band. A shift of the m
CN band by 140 cmÀ1 to lower wave num-
The reproducible formation and coordination of perrhenate in
the product was unexpected, but is not unusual in the coordination
bers with respect to uncoordinated HLdiethyl is due to the coordina-
tion of the ligand. A band of medium intensity at 1072 cmÀ1 can be
assigned to the ReN triple bond. Two intense bands at 921 and
860 cmÀ1 result from the coordinated perrhenate, which normally
can be identified by two or three IR bands in the range of 930–
860 cmÀ1 depending on the symmetry of the coordination mode
[24].
À
chemistry of rhenium. It is frequently observed, when ReO4 is
formed as a side-product of the complex formation and an addi-
tional mononegative ligand is required for charge compensation
[17–23].
The bond between Re1 and O1 of 2.348(5) Å is remarkably long
for a ReO single bond. This is due to the strong trans influence of
the triple-bonded nitrido ligand. The Re2–O1 bond length of
1.734(5) Å is slightly lengthened as a consequence of the coordina-
tion, while the Re2–O2, Re2–O3 and Re2–O4 bonds clearly show
The origin of the perrhenate ligand is doubtlessly a hydrolytic
oxidation during the complex formation. The yields, which are ob-
tained, are reproducibly higher than 50% with regards to Re, which
is by far too high to be explained by some impurities in the starting
material [ReNCl2(PPh3)2], which has additionally be excluded by
careful inspection of the IR spectrum of this precursor. The forma-
tion of perrhenate from a nitrido compound is unexpected, but not
without precedent. Some reactions are reported, where chlorido li-
gands of [ReNCl2(PMe2Ph)3] or [ReNCl2(PPh3)2] were abstracted
after the addition of base and the ‘undercoordinated’ metal ion
was stabilized by subsequent oxidation and hydrolysis, which fi-
nally results in the formation of perrhenate [21,22]. In some rare
cases, the isolation and structural characterization of compounds
containing one important intermediate of such reactions, trioxido-
nitridorhenate(VII) (ReO3N)2À, succeeded [25,26]. This building
block readily hydrolyses under the formation of perrhenate.
Summarizing, it can be stated that the new tridentate phos-
phines HLdiethyl and HLmorph are suitable as mononegative ligands
and form stable oxorhenium(V) and nitridorhenium(V) complexes.
3. Experimental
(NBu4)[ReOCl4] [27], [ReNCl2(PPh3)2] [28], and 2-(diphenyl-
phosphinomethyl)aniline H2L1 [29] were prepared by literature
procedures. IR spectra were measured as KBr pellets on a Shimadzu
FTIR-spectrometer 8300. ESI mass spectra were measured with an
Agilent 6210 ESI-TOF. All MS results are given in the form: m/z,
assignment. Elemental analysis of carbon, hydrogen, nitrogen,
and sulfur were determined using a Heraeus vario EL elemental
Fig. 2. Ellipsoid representation [31] of the molecular structure of [ReN-(OReO3)-
(PPh3)-(Ldiethyl)]. Thermal ellipsoids represent 50% probability. H atoms have been
omitted for clarity.

J. Schroer, U. Abram / Polyhedron 33 (2012) 218–222
221
analyzer. NMR spectra were taken with a JEOL 400 MHz multinu-
clear spectrometer.
ture was kept for crystallization. The product deposited as emerald
green crystals. Yield (based on Re): 58% (45 mg). Anal. Calc. for
C
31H31Cl2N3OSPRe: C, 47.63; H, 4.00; N, 5.38; S, 4.10. Found: C,
47.52; H, 3.67; N, 5.16; S, 4.08%. IR (m
max, cmÀ1): 1523 st (C@N),
3.1. HLdiethyl
968 st (Re@O). 1H NMR (CDCl3, d, ppm): 1.38 (m, 6H, 2CH3), 3.58
(m, 1H, NCH2), 3.81 (m, 1H, NCH2), 4.28 (m, 2H, PCH2), 4.49 (m,
1H, NCH2), 4.99 (m, 1H, NCH2), 6.59–7.62 (m, 19H, Ph). 31P NMR
(CDCl3, d, ppm): 5.7. +ESI MS (m/z): 742.17 [MÀ2Cl+OMe]+.
A solution of NEt3 (280 lL, 2 mmol) in 2 mL THF was added to a
solution of 2-(diphenylphosphinomethyl)aniline (582 mg, 2 mmol)
and diethylthiocarbamoylbenzimidoyl chloride (509 mg, 2 mmol)
in 3 mL THF under an atmosphere of dry argon at 0 °C under vigor-
ous stirring. After 1 h, the reaction mixture was heated to 50 °C and
stirred for another 1.5 h. The resulting triethylammonium chloride
was filtered off and the solvent was removed in vacuum. Ethanol
was added to the remaining residue under vigorous stirring. This
gave a pale yellow powder, which was filtered off and dried under
vacuum. Yield: 78% (800 mg). Anal. Calc. for C31H32N3SP: C, 73.06;
H, 6.33; N, 8.24; S, 6.29. Found: C, 72.59; H, 5.96; N, 7.94; S, 5.93%.
3.4. [ReOCl(Lmorph)]
HLmorph (52 mg, 0.1 mmol) was added to a solution of (NBu4)-
[ReOCl4] (59 mg, 0.1 mmol) in 4 mL methanol. A deep green
solution was obtained immediately, which was stirred at room
temperature until the product precipitated as a green solid. Crys-
tals, which were suitable for X-ray crystallography, were obtained
from acetone. Yield (based on Re): 58% (45 mg). Anal. Calc. for
IR (m
max, cmÀ1): 3325 w (N–H), 1612 st (C@N). 1H NMR (DMSO, d,
ppm): 1.13 (t, 3H, CH3, J = 6.9 Hz), 1.18 (t, 3H, CH3, J = 7.1 Hz), 3.69
(q, 2H, CH2, J = 6.9 Hz), 3.77 (s, 2H, PCH2), 3.85 (q, 2H, CH2,
J = 7.1 Hz), 6.96–7.15 (m, 4H, Ph), 7.41–7.63 (m, 14H, Ph), 10.17
(s, 1H, NH). 31P NMR (CDCl3, d, ppm): À17.3. +ESI MS (m/z):
508.20 [M+H]+.
C
31H29Cl2N3OSPRe: C, 46.79; H, 3.67; N, 5.28; S, 4.03. Found: C,
46.93; H, 3.12; N, 5.41; S, 4.27%. IR (
m
max, cmÀ1): 1512 st (C@N),
972 st (Re@O). 1H NMR (DMSO, d, ppm): 3.80 (m, 4H, 2CH2), 4.21
(m, 2H, NCH2), 4.39 (m, 4H, PCH2, NCH2), 4.75 (m, 1H, CH2), 5.20
(m, 1H, NCH2), 6.53 (m, 1H, Ph), 6.69 (m, 1H, Ph), 7.23–7.99 (m,
17H, Ph). 31P NMR (CDCl3, d, ppm); 7.1. +ESI-MS (m/z): 756.14
[MÀ2Cl+OMe]+.
3.2. HLmorph
The compound was prepared as described for HLdiethyl by using
morpholinylthiocarbamoylbenzimidoyl chloride (538 mg, 2 mmol)
instead of the diethyl derivative. Yield: 86% (900 mg). Anal. Calc. for
3.5. [ReN(OReO3)(PPh3)(Ldiethyl)]
A solution of HLdiethyl (51 mg, 0.1 mmol) in 5 mL CH2Cl2 was
C
31H30N3SOP: C, 71.11; H, 5.77; N, 8.02; S, 6.12. Found: C, 70.76; H,
dropwise added to
a suspension of [ReNCl2(PPh3)2] (80 mg,
5.43; N, 7.73; S, 5.85%. IR (m
max, cmÀ1): 3337 w (N–H), 1628 st
0.1 mmol) in 5 mL CH2Cl2. After stirring for 1 h at room tempera-
ture, three drops NEt3 were added. An orange-brown solution
was obtained after stirring for two more hours. For crystallization,
the solution was overlayered with methanol. The product was iso-
lated as orange-brown crystals. Yield (based on Re): 57% (35 mg).
Anal. Calc. for C49H46N4O4SP2Re2: C, 48.18; H, 3.79; N, 4.59; S,
(C@N). 1H NMR (DMSO, d, ppm): 3.52 (t, 2H, CH2, J = 4.4 Hz), 3.57
(t, 2H, CH2, J = 4.4 Hz), 3.94 (t, 2H, CH2, J = 4.4 Hz), 6.96–7.11 (m,
4H, Ph), 7.32–7.52 (m, 15H, Ph), 9.99 (s, 1H, NH). 31P NMR (CDCl3,
d,
ppm): À16.9. +ESI MS (m/z): 524.19 [M+H]+, 546.18 [M+Na]+,
563.17 [M+K]+.
2.63. Found: C, 47.93; H, 3.30; N, 4.21; S, 2.93%. IR (m
max, cmÀ1):
3.3. [ReOCl2(Ldiethyl)]
1473 st (C@N), 1095 st (Re„N), 921 st, 860 st (ReO4À). 1H NMR
(CDCl3, d, ppm): 1.34 (m, 6H, 2CH3), 3.59 (m, 1H, NCH2), 3.80 (m,
1H, NCH2), 4.28 (m, 2H, PCH2), 4.51 (m, 1H, NCH2), 4.98 (m, 1H,
NCH2), 6.43–7.94 (m, 19H, Ph). 31P NMR (CDCl3, d, ppm): 21.6,
46.0. +ESI-MS (m/z): 971.25 [MÀReO4]+, 1221.19 [M+H]+, 1243.19
[M+Na]+.
HLdiethyl (51 mg, 0.1 mmol) dissolved in 2 mL CH2Cl2 was added
to a solution of (NBu4)[ReOCl4] (59 mg, 0.1 mmol) in 2 mL CH2Cl2.
The solution immediately became emerald green. It was stirred for
2 h at room temperature. Acetone (4 mL) was added and the mix-
Table 3
X-ray structure data collection and refinement parameters.
[ReOCl2(Ldiethyl)]
[ReOCl2(Lmorph)]Á2acetone
[ReN(OReO3)(PPh3)(Ldiethyl)]Á0.5CH2Cl2
Formula
Mw
Crystal system
a (Å)
b (Å)
c (Å)
C31H31Cl2N3OSPRe
781.49
orthorhombic
33.318(2)
30.267(2)
12.376(1)
90
C37H41Cl2N3O4SPRe
C49.5H47CIN4O4P2SRe
1263.76
triclinic
12.049(1)
12.274(1)
19.040(2)
98.20(1)
911.86
monoclinic
15.281(2)
15.252(1)
16.642(1)
90
a
(°)
b (°)
90
90
12480(2)
Fdd2
107.46(1)
90
3700.0(7)
P21/c
101.54(1)
112.39(1)
2475.4(4)
c
(°)
V (Å3)
ꢀ
Space group
P1
Z
16
1.664
4.213
4
2
Dcalc (g cmÀ3
)
1.637
3.572
1.696
5.093
l
(mmÀ1
)
Absorption correction
Tmin
Tmax
No. of reflection
No. of independent
No. of parameters
R1/wR2
integration
0.4043
0.6698
38620
8393
361
integration
0.5936
0.8478
18348
7792
447
0.0534, 0.1230
0.833
integration
0.4151
0.7101
25981
13220
594
0.0347, 0.0766
1.108
0.0500, 0.1243
0.999
Good-of-fit (GoF)

222
J. Schroer, U. Abram / Polyhedron 33 (2012) 218–222
[9] J. Schroer, U. Abram, Polyhedron 28 (2009) 2277.
3.6. X-ray structure determinations
[10] J. Schroer, U. Abram, Inorg. Chem. Commun. 13 (2010) 26.
[11] H.H. Nguyen, V.M. Deflon, U. Abram, Eur. J. Inorg. Chem. (2009) 3179.
[12] H.H. Nguyen, P.I. da, S. Maia, V.M. Deflon, U. Abram, Inorg. Chem. 48 (2009) 25.
[13] H.H. Nguyen, J.J. Jegathesh, P.I. da, S. Maia, V.M. Deflon, R. Gust, S. Bergemann,
U. Abram, Inorg. Chem. 48 (2009) 9356.
[14] L. Beyer, R. Widera, Tetrahedron Lett. 23 (1982) 1881.
[15] L. Beyer, J. Hartung, R. Widera, Tetrahedron 40 (1984) 405.
[16] (a) J. Hartung, G. Weber, L. Beyer, R. Szargan, Z. Anorg. Allg. Chem. 523 (1985)
153;
The intensities for the X-ray determinations were collected on a
STOE IPDS automated single crystal diffractometer with MoK
a
radiation at 200 K. The structures were solved by Patterson meth-
ods using SHELXS-97 [30]. Subsequent Fourier-difference map analy-
ses yielded the positions of the non-hydrogen atoms. Refinement
was performed using SHELXL-97 [30]. Hydrogen atoms were calcu-
lated for idealized positions and treated with the ‘riding model’ op-
tion of SHELXL. Crystal data and more details of the data collections
and refinements are contained in Table 3.
(b) U. Abram, R. Münze, J. Hartung, L. Beyer, R. Kirmse, K. Köhler, J. Stach, H.
Behm, P.T. Beurskens, Inorg. Chem. 28 (1989) 834;
(c) U. Abram, R. Hübener, Inorg. Chim. Acta 206 (1993) 23;
(d) L. Beyer, J.J. Criado, E. Garcia, F. Lessmann, M. Medarde, R. Richter, E.
Rodriguez, Tetrahedron 52 (1996) 6233;
(e) J.J. Criado, E. Rodriguez-Fernandez, E. Garcia, M.R. Hermosa, E. Monte, J.
Inorg. Biochem. 69 (1998) 113;
(f) J. Sieler, R. Richter, L. Beyer, O. Lindqvist, L. Anderson, Z. Anorg. Allg. Chem.
41 (1984) 515;
Appendix A. Supplementary data
CCDC 846928, 846929 and 846930 contains the supplementary
crystallographic data for [ReOCl2(Ldiethyl)], [ReOCl2(Lmorph)]Á2ace-
tone and [ReN(OReO3)(PPh3)(Ldiethyl)]Á0.5CH2Cl2. These data can
be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/
retrieving.html, or from the Cambridge Crystallographic Data Cen-
tre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-
033; or e-mail: deposit@ccdc.cam.ac.uk.
(g) F. Yaoting, L. Huije, H. Honwei, Z. Zhengmin, Z. Qinghuan, Z. Linpin, C.
Fenghong, J. Coord. Chem. 65 (2000) 50.
[17] (a) H.H. Nguyen, PhD Thesis, Freie Universität, Berlin, 2009.;
(b) J.D. Castillo Gomez, M.Sc Thesis, Freie Universität, Berlin, 2010.
[18] M. Göldner, L. Galich, U. Cornelissen, H. Homborg, Z. Anorg. Allg. Chem. 626
(2000) 985.
[19] P.D. Benny, C.L. Barnes, P.M. Piekarski, J.D. Lydon, S.S. Jurisson, Inorg. Chem. 42
(2003) 6519.
[20] P. Perez-Lourido, J. Romero, J. Garcia-Vazquez, A. Sousa, K.P. Maresca, D.J. Rose,
J. Zubieta, Inorg. Chem. 37 (1998) 3331.
[21] U. Abram, A. Voigt, R. Kirmse, Polyhedron 19 (2000) 1741.
[22] U. Abram, A. Voigt, R. Kirmse, R. Hübener, R. Carballo, E. Vazquez-Lopez, Z.
Anorg. Allg. Chem. 624 (1998) 1662.
[23] S.B. Seymore, S.N. Brown, Inorg. Chem. 45 (2006) 9540.
[24] M.C. Chakravorti, Coord. Chem. Rev. 106 (1990) 205.
[25] H. Braband, E. Yegen, E. Oehlke, U. Abram, Z. Anorg. Allg. Chem. 631 (2005)
2408.
[26] H. Braband, E. Oehlke, U. Abram, Z. Anorg. Allg. Chem. 632 (2006) 1051.
[27] R. Alberto, R. Schibli, A. Egli, P.A. Schubiger, W.A. Hermann, G. Artus, U. Abram,
T.A. Kaden, J. Organomet. Chem. 493 (1995) 119.
[28] P. Sullivan, J.C. Brewer, H.B. Gray, Inorg. Synth. 92 (1992) 146.
[29] J. Schroer, S. Wagner, U. Abram, Inorg. Chem. 49 (2010) 10694.
[30] G.M. Sheldrick, SHELXS86 and SHELXL97 – A Programme Package for the Solution
and Refinement of Crystal Structures, University of Göttingen, Germany, 1997.
[31] L.J. Farrugia, J. Appl. Crystallogr. 30 (1997) 565.
References
[1] R. Alberto, Technetium, in: J.A. McCleverty, T.J. Mayer (Eds.), Comprehensive
Coordination Chemistry II, vol. 5, Elsevier, Amsterdam, The Netherlands, 2003,
p. 127.
[2] U. Abram, Rhenium, in: J.A. McClevery, T.J. Mayer (Eds.), Comprehensive
Coordination Chemistry II, vol. 5, Elsevier, Amsterdam, The Netherlands, 2003,
p. 271.
[3] U. Abram, R. Alberto, J. Braz. Chem. Soc. 17 (2006) 1486.
[4] Shuang Liu, S. Chakraborty, Dalton Trans. 40 (2011) 6077.
[5] C. Bolzati, A. Refosco, A. Marchiani, P. Ruzza, Curr. Med. Chem. 17 (2010) 2656.
[6] J.D.G. Correia, A. Domingos, I. Santos, H. Spies, J. Chem. Soc., Dalton Trans.
(2001) 2245.
[7] C. Fernandes, T. Kniess, L. Gano, S. Seifert, H. Spies, I. Santos, Nucl. Med. Biol. 31
(2004) 785.
[8] H.H. Nguyen, J. Grewe, J. Schroer, B. Kuhn, U. Abram, Inorg. Chem. 47 (2008)
5136.