Diastereomeric halfsandwich rhenium complexes containing hemilabile phosphane ligands

Article abstract of DOI:10.1002/ejic.200400552

The syntheses and some typical reactions of diastereomeric rhenium complexes [CpRe(NO)(CO){P(Ph)(R)(R′)}]BF₄ (R = Me, Ph; R′ = 2-C₆H₄OMe, CH₂C₄H₂S, CH₂C₄H₇O

Full text of DOI:10.1002/ejic.200400552

FULL PAPER
Diastereomeric Halfsandwich Rhenium Complexes Containing Hemilabile
Phosphane Ligands[‡]
Stefan Dilsky[a] and Wolfdieter A. Schenk*[a]
Dedicated to Professor Johann Weis on the occasion of his 60th birthday
Keywords: Rhenium / Chiral complexes / Chiral P ligands / Hemilabile P ligands / Sandwich complexes
The syntheses and some typical reactions of diastereomeric
rhenium complexes [CpRe(NO)(CO){P(Ph)(R)(RЈ)}]BF4 (R =
Me, Ph; RЈ = 2-C6H4OMe, CH2C4H3S, CH2C4H7O) (3a−e) are
described. Reduction of the carbonyl ligand with NaBH4
in THF gave the corresponding methyl complexes
[CpRe(NO){P(Ph)(R)(RЈ)}(CH3)] (4a−e). Acid treatment of the
with RЈ = 2-C6H4OMe (5a, d) decomposed in solution at room
temperature. In donor solvents, the chelate ring opens giving
the stable solvated complexes [CpRe(NO){P(Ph)(R)(RЈ)}]-
(solvent)]BF4 (solvent
= CH3CN, THF) (6b−e, 7d). The
new compounds are thus suitable starting materials for
the syntheses of diastereomeric rhenium complexes
methyl complexes leads to liberation of methane and coor- [CpRe(NO){P(Ph)(R)(RЈ)}(L)]BF4.
dination of the additional donor site of the potentially bident-
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
ate phosphane ligand. Of the chelate complexes 5a−e, those
Germany, 2004)
Introduction
Results
Phosphane Synthesis
Since the first successful enantiomer separation of the
pseudotetrahedral at-metal chiral complex [CpMn(CO)-
(NO)(PPh3)]PF6 by Brunner,[1] a large variety of different
at-metal chiral, kinetically stable or labile complexes has
been synthesised. Some of them have been of synthetic
interest, e.g. (RFe)-[CpFe(CO)(PPh3){C(O)Me}] which has
been used, inter alia, in the total synthesis of Captopril.[2,3]
Other complexes of this type were investigated as potential
catalysts[2] and the chiral Lewis acidic rhenium complex
[CpRe(NO)(PPh3)]ϩ has been studied in great detail by
Gladysz et al.[4,5] We have recently extended this work to
thiolate and thioaldehyde complexes of [CpRe(NO)-
(PPh3)]ϩ and its congeners [CpRe(NO){P(OPh)3}]ϩ and
The hemilabile ligands which are central to this study are
shown in Scheme 1.
[CpRe(NO){P(iPr)3}]ϩ.[6Ϫ9] By introducing
a
second
stereogenic centre at the phosphane ligand, higher selec-
tivities in reactions at coordinated ligands might be
achieved. Moreover, by introducing a second donor atom
into the phosphane, a hemilabile[10,11] ligand can be created
which should serve to stabilise reactive intermediates.
Scheme 1
The prototypic 1a is commercially available, whereas 1b
was obtained by a slight modification of a known[12] syn-
thesis as follows. Cleavage of PPh3 with lithium in THF and
alkylation of the resultant lithium diphenylphosphide with
2-(chloromethyl)thiophene gave 1b in 87% yield. C-chiral
racemic 1c has been obtained previously via a similar ap-
proach.[13] Cleavage of bis(2-anisyl)phenylphosphane with
sodium in liquid ammonia followed by alkylation with
methyl iodide gave the P-chiral racemic ether phosphane
ligand 1d[14] in 63% yield. Deprotonation of methylphen-
ylphosphane with butyllithium in THF followed by alky-
[‡]
Enantioselective Organic Syntheses with Chiral Transition
Metal Complexes, 13. For part 12 see: G. Bringmann, A.
Wuzik, J. Kümmel, W. A. Schenk, Organometallics 2001, 20,
1692Ϫ1694.
[a]
Institut für Anorganische Chemie der Universität Würzburg,
Am Hubland, 97074 Würzburg, Germany
Fax: (internat.) ϩ 49-931-8884605
E-mail: wolfdieter.schenk@mail.uni-wuerzburg.de
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DOI: 10.1002/ejic.200400552
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S. Dilsky, W. A. Schenk
FULL PAPER
lation with 2-(chloromethyl)thiophene gave P-chiral 1e
(73%).
The phosphanes 1a, 1b and 1d are colourless solids which
are readily soluble in most organic solvents. They can be
recrystallised from alcohols or saturated hydrocarbons and
may be handled in air for short periods of time. Compound
1c had been reported as a waxy solid, whereas the phos-
phane 1e is a colourless, air-sensitive oil with an unpleasant
odour. The 31P NMR signals are shifted to high field as the
number of alkyl substituents increases. The methylene
group of 1e can be observed as an ABX system with
(1)
2
2JH,H ϭ 14.4 Hz and JP,H ϭ 3.6 Hz.
Compounds 3d and 3e were obtained as 1:1 mixtures of
diastereoisomers, i.e. ReϪP bond formation proceeds with-
out diastereoselectivity. All new complexes [CpRe(CO)-
(NO)(PR3)]BF4 (3aϪe) are yellow to yellow-brown air-
stable solids (e.g. 3d melts in air without decomposition).
While 3c is soluble in THF, 3b and 3d are insoluble in THF
and 3e is insoluble even in acetone. Due to the stereogenic
metal centre, the PCH2-protons in 3b can be observed as
Crystal and Molecular Structure of 1b·BH3
Compound 1b was converted into its borane adduct by
treatment with BH3·SMe2 in THF. Recrystallisation from
ethanol/hexane gave crystals suitable for a single-crystal X-
ray structure determination (Figure 1).
2
2
an ABX system with JH,H ϭ 15 Hz and JP,H ϭ 10 Hz.
Diastereomeric 3e exhibits two such sets of signals. The 31
P
NMR signals are shifted 25 to 30 ppm downfield compared
with the free ligand. The CO and NO stretching frequencies
appear in the ranges expected for cationic complexes of
this kind.
Crystal and Molecular Structures of 3a, 3b and 3d؊AlF4
Three of the new complexes were investigated by X-ray
diffraction. Figure 2Ϫ4 show views of the cations.
Figure 1. Molecular structure of PPh2(CH2C4H3S)·BH3 (1b·BH3),
hydrogen atoms omitted for clarity. Space group Pna21; selected
distances [pm] and angles (°) (standard deviations in parentheses):
P(1)ϪB(1) 190.4(4), P(1)ϪC(1) 182.9(3), P(1)ϪC(10) 181.2(3),
P(1)ϪC(20)
180.6(3);
C(1)ϪP(1)ϪB(1)
111.98(19),
C(10)ϪP(1)ϪB(1) 110.52(17), C(20)ϪP(1)ϪB(1) 117.02(17),
C(1)ϪP(1)ϪC(10) 105.82(16), C(1)ϪP(1)ϪC(20) 104.13(17),
C(10)ϪP(1)ϪC(20) 106.58(15)
As expected, the BH3 group is bound to phosphorus
rather than to the sulfur atom of the thiophene moiety. The
PϪB and PϪC bond lengths are in agreement with those of
similar borane adducts.[15,16] The angles at the tetrahedral
phosphorus atom are slightly distorted reflecting the low
electronegativity of the BH3 substituent.
Figure 2. Structure of the cation of [CpRe(CO)(NO){PPh2(2-
C6H4OMe)}]BF4 (3a), hydrogen atoms omitted for clarity. Space
group P21/c; selected distances [pm] and angles (°) (standard devi-
ations in parentheses): Re(1)ϪC(10) 228.2(7), Re(1)ϪC(11)
Carbonyl Complexes
229.7(6),
Re(1)ϪC(12)
231.8(6),
Re(1)ϪC(13)
229.9(6),
Re(1)ϪC(14) 229.9(7), Re(1)ϪC(1) 191.6(6), Re(1)ϪN(1) 180.1(6),
Re(1)ϪP(1)
239.26(14);
178.8(5),
Re(1)ϪC(1)ϪO(1)
N(1)ϪRe(1)ϪC(1)
175.1(6),
97.2(3),
The chiral racemic rhenium complex [CpRe(CO)-
(NO)(NCCH3)]BF4 (2) was the common starting material
for the following syntheses and is readily accessible from
[Re2(CO)10] in three steps.[4] The acetonitrile ligand is
Re(1)ϪN(1)ϪO(3)
P(1)ϪRe(1)ϪN(1) 91.37(17), P(1)ϪRe(1)ϪC(1) 88.32(18)
Due to the similar sizes of the CO and NO ligands these
known to be easily replaceable by phosphanes[7,17,18] and two groups are usually disordered.[19] Since the extent of
this methodology was also successful with the phosphanes this disorder is variable, the apparent ReϪC and ReϪN
1aϪe [Equation (1)].
bond lengths can vary from their normal values as in 3a to
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Rhenium Complexes with Hemilabile Phosphane Ligands
FULL PAPER
rhenium atoms are octahedrally surrounded with the cyclo-
pentadienyl ligand serving as a six-electron donor. In 3a
and 3dϪAlF4, the N(1)ϪRe(1)ϪC(1) angles are signifi-
cantly larger [97.2(3)° and 95.8(3)°, respectively] than in 3b
[92.4(2)°]. As the structure of the prototypic
[CpRe(CO)(NO)(PPh3)]ϩ reveals the same widened
N(1)ϪRe(1)ϪC(1) angle [95.5(5)°],[20] we have to conclude
that the angle in 3b is abnormally small. This is surprising
since the phosphorus ligands of this study all have similar
steric and electronic properties.
Ϫ
The surprising appearance of AlF4 as a counterion in
the structure of 3dϪAlF4 was traced back to an impurity in
the [NO]BF4 which was used in the synthesis of [CpRe-
(CO)(NO)(NCCH3)]BF4 (2).
Methyl Complexes
The hydride reduction of a ReϪCO group has already
been described by Gladysz,[4,17] Casey,[21] Graham[22] and
our group.[7] The new methyl complexes 4aϪe were ob-
tained in the same way in good yields as orange or orange-
red solids [Equation (2)].
Figure 3. Structure of the cation of [CpRe(CO)(NO){PPh2-
(CH2C4H3S)}]BF4 (3b), hydrogen atoms omitted for clarity. Space
¯
group P1; selected distances [pm] and angles (°) (standard devi-
ations in parentheses): Re(1)ϪC(10) 231.4(5), Re(1)ϪC(11)
227.8(6),
Re(1)ϪC(12)
227.1(6),
Re(1)ϪC(13)
228.1(6),
Re(1)ϪC(14) 231.5(5), Re(1)ϪC(1) 188.4(5), Re(1)ϪN(1) 182.6(4),
Re(1)ϪP(1)
Re(1)ϪN(1)ϪO(2)
P(1)ϪRe(1)ϪN(1) 95.56(14), P(1)ϪRe(1)ϪC(1) 89.70(16)
239.05(12);
175.7(4),
Re(1)ϪC(1)ϪO(1)
N(1)ϪRe(1)ϪC(1)
179.7(5),
92.4(2),
(2)
Complexes 4aϪe are readily soluble in common organic
solvents except aliphatic hydrocarbons. This again makes a
separation of the diastereomeric complexes 4cϪe difficult.
Nevertheless, a diastereomeric excess of 35% was achieved
during the workup of 4e. This helped in the assignment of
the spectroscopic data of the two diastereoisomers. Charac-
teristic spectroscopic features for all methyl complexes are
the low frequency of the NO stretching vibration and the
high-field shift of the ReϪCH3 resonance in 13C NMR
spectroscopy. Furthermore, the phosphorus resonances are
shifted downfield compared with those of the cationic start-
ing materials.
Figure 4. Structure of the cation of [CpRe(CO)(NO){P(Ph)(Me)(2-
C6H4OMe)}]AlF4 (3d-AlF4), hydrogen atoms omitted for clarity.
Space group P21/n; selected distances [pm] and angles (°) (standard
deviations in parentheses): Re(1)ϪC(10) 231.7(7), Re(1)ϪC(11)
229.3(7),
Re(1)ϪC(12)
227.7(7),
Re(1)ϪC(13)
229.4(7),
Re(1)ϪC(14) 227.5(7), Re(1)ϪC(1) 186.2(6), Re(1)ϪN(1) 183.3(7),
Re(1)ϪP(1)
239.65(17);
Re(1)ϪC(1)ϪO(1)
N(1)ϪRe(1)ϪC(1)
173.1(7),
95.8(3),
Re(1)ϪN(1)ϪO(2)Ϫ176.3(8),
P(1)ϪRe(1)ϪN(1) 89.6(2), P(1)ϪRe(1)ϪC(1) 91.1(2)
almost equal values as in 3d. The topological similarity of
the CO and NO ligands also thwarted any attempts to sep-
arate the diastereoisomers of 3cϪe by crystallisation. More-
Crystal and Molecular Structure of 4d
Crystals of the unlike isomer (RRe,SP/SRe,RP)-4d suitable
over, the disorder makes it impossible to determine the rela- for X-ray diffraction were grown at Ϫ30 °C by layering a
tive configuration of the cation of 3dϪAlF4. toluene solution of the diastereomeric mixture with petro-
Neither the NO ligands are bent nor are the cyclopen- leum ether. A comparison of this structure with those of
tadienyl ligands slipped in any of the three structures. The similar alkyl complexes (e.g. [CpRe(NO){P(iPr)3}(CH3)][7]
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and [CpRe(NO)(PPh3)(CH2Ph)][23]) did not reveal any sig- [CpRe(NO){P(iPr)3}(CH3)] [218.2(5)].[7] The cyclopen-
nificant differences (Figure 5).
tadienyl ligand is slightly slipped such that the two carbon
atoms which are approximately trans to the strongly π-ac-
cepting NO ligand have moved about 8 pm away from the
rhenium atom. As in [CpRe(NO){P(iPr)3}(CH3)] and
[CpRe(NO)(PPh3)(CH2Ph)], the N(1)ϪRe(1)ϪC(1) angle is
widened [95.55(18)°], although the NO and CH3 ligands are
the smallest substituents.
Chelate Ring Closure
It is known that methylrhenium complexes liberate meth-
ane when treated with acids.[5,24,25] In the absence of do-
nors, the solvent dichloromethane stabilises the resultant 16
valence electron complex. The CH2Cl2 complex thus ob-
tained served as a starting material for a variety of com-
pounds,[5] although it tends to undergo side reactions[6,26]
and to decompose above Ϫ20 °C.[24,26] The phosphane li-
gands in this study offer donor functionalities (e.g. oxygen
or sulfur), which should serve to stabilise the complex by
intramolecular coordination. When the methyl complexes
were treated with HBF4 in dichloromethane, three com-
plexes with chelate structures could be isolated, namely 5b,
5c and 5e [Equation (3)].
Figure 5. Molecular structure of (RRe,SP/SRe,RP) [CpRe(NO){P-
(Ph)(Me)(2-C6H4OMe)}(CH3)] (4d), hydrogen atoms omitted for
¯
clarity. Space group P1; selected distances [pm] and angles (°)
(standard deviations in parentheses): Re(1)ϪC(10) 228.4(4),
Re(1)ϪC(11) 234.0(4), Re(1)ϪC(12) 233.6(4), Re(1)ϪC(13)
225.7(4), Re(1)ϪC(14) 222.8(4), Re(1)ϪC(1) 214.1(4), Re(1)ϪN(1)
175.6(3), Re(1)ϪP(1) 234.30(9); Re(1)ϪN(1)ϪO(1) 177.9(3),
N(1)ϪRe(1)ϪC(1) 95.55(18),
P(1)ϪRe(1)ϪC(1) 90.24(12)
P(1)ϪRe(1)ϪN(1) 88.89(11),
(3)
The P(1)ϪRe(1) bond in 4d is 3 pm shorter than in
[CpRe(NO){P(iPr)3}(CH3)] and even 2 pm shorter than in
[CpRe(NO)(PPh3)(CH2Ph)], reflecting the smaller size of
the phosphane ligand. Moreover, the C(1)ϪRe(1) distance
is remarkably shorter [214.1(4) pm] than in
Figure 6. 31P NMR spectra of the complexes [CpRe(NO){PPh2(CH2C4H3S)}(X)]Y; X ϭ CO, Y ϭ BF4 3b, X ϭ CH3, Y ϭ Ϫ4b, X ϭ Ϫ,
Y ϭ BF4 5b
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Rhenium Complexes with Hemilabile Phosphane Ligands
FULL PAPER
Attempts to obtain ring-closed products from the anisyl- cess is slowed down by the hemilabile ligand, compared
substituted phosphane complexes 4a and 4d were only par- with the rapid decomposition of [CpRe(NO)(PPh3)-
tially successful (see below). Two different samples of 4e (ClCH2Cl)]BF4.[24]
with 0 and 34% de, respectively, were employed in this reac-
tion in order to gain some insight into the stereochemistry
of the demethylation step. In both cases the de was retained
Stabilitiy of the Ring-Closed Complexes and Preparation of
in the product 5e.
Solvated Complexes
Although no crystals suitable for X-ray diffraction could
be grown, the ring closure can be unambiguously inferred
from 31P NMR spectroscopic data. It is known that in che-
late complexes the phosphorus chemical shift depends on
the ring size. For five-membered rings, an additional
20Ϫ30 ppm downfield shift is typical.[27,28] The 31P NMR
spectra of 5b, 5c and 5e exhibit this feature, an example is
shown in Figure 6. The NO stretching frequency was found
in the typical range for cationic ether[29] or thioether[6,30,31]
complexes of the general formula [CpRe(NO)(PR3)(L)]ϩ.
All other spectroscopic data are also in agreement with a
cationic structure.
In the acid-promoted ring closure reactions of 5c and 5e,
no diastereoselectivity was observed thus so far ruling out
the possibility of a kinetic diastereoisomeric enrichment. If
the diastereomeric complexes differ in energy, a thermo-
dynamic enrichment might be possible. To check this, com-
plexes 5b, 5c and 5e were dissolved in polar solvents (e.g.
THF, acetone or acetonitrile at 20 °C or reflux) and the
mixtures analysed by 31P NMR spectroscopy. While the
acetone solutions did not show any enrichment or de-
composition even after being heated to reflux for 24 h, a
small diastereomeric enrichment was observed for 5e in
THF. Due to the different solubility of the diastereomers,
only a suspension of 5e in THF could be obtained with one
diastereomer preferentially dissolved. The extraction of 5e
with THF led to a de of 60%, allowing the assignment of
the spectroscopic data to the respective isomers. Upon dis-
solving the complexes in acetonitrile, new upfield signals in
the 31P NMR spectra appeared immediately. After 4 h, only
the upfield signals remained. NMR and IR spectroscopic
analyses suggested a ring-opening with the acetonitrile oc-
cupying the vacated coordination site as shown for 6b, 6c
and 6e [Equation (4)].
The reaction of 4d with HBF4 was investigated by low-
temperature NMR spectroscopy. The phosphorus spectrum
at Ϫ50 °C shows, aside from the expected downfield signals
of two diastereomeric ring-closed complexes, a second pair
of signals belonging to a cationic, ring-opened complex.
Raising the temperature to 20 °C led to a decrease of the
downfield signals and an increase of the upfield signals.
Continued measurements at 20 °C revealed a slow decrease
of both signal sets and, after 24 h, none of the signals could
be observed any more. This can be interpreted in terms of
a low stability of the ring-closed complex. At temperatures
around Ϫ30 °C, there seems to be an equilibrium between
ring-closed and ring-opened species, were the dichlorometh-
ane solvent acts as a ligand. The dichloromethane complex
slowly decomposes at temperatures above Ϫ20 °C and is
removed from the equilibrium which eventually leads to
complete decomposition (Scheme 2). Nevertheless, this pro-
(4)
Crystal and Molecular Structure of 6e
The compositions of the acetonitrile complexes were cor-
roborated by X-ray crystallography. Suitable crystals of the
unlike diastereomer (RRe,SP/SRe,RP)-[CpRe(NO){P(Ph)-
(Me)(CH2C4H3S)}(NCCH3)]BF4 (6e) were obtained at 20
°C by layering a THF solution of the diastereomeric mix-
ture with hexane. Figure 7 shows a view of the cation.
Scheme 2
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Figure 8. Disorder in the structure of unlike-6e; the phosphane li-
gand is reflected along an imaginary mirror plane which contains
the Cp centre, the rhenium atom and two carbon atoms of the
thiophene moiety giving rise to the like diastereoisomer
Figure 7. Structure of the cation of (RRe,SP/SRe,RP)-
[CpRe(NO){P(Ph)(Me)(CH2C4H3S)}(NCCH3)]BF4 (6e), hydrogen
atoms omitted for clarity. Space group P21/c; selected distances
[pm] and angles (°) (standard deviations in parentheses):
Re(1)ϪC(10) 222.3(8), Re(1)ϪC(11) 228.3(8), Re(1)ϪC(12)
231.9(8),
Re(1)ϪC(13)
226.9(7),
Re(1)ϪC(14)
221.6(8),
Re(1)ϪN(1) 205.5(6), Re(1)ϪN(2) 176.0(6), Re(1)ϪP(1A) 236.3(2);
Re(1)ϪN(2)ϪO(1)
N(1)ϪC(1)ϪC(2)
178.9(5),
178.6(8),
Re(1)ϪN(1)ϪC(1)
N(1)ϪRe(1)ϪN(2)
176.9(6),
96.9(2),
Crystal and Molecular Structure of 7d
P(1A)ϪRe(1)ϪN(1) 85.03(17), P(1A)ϪRe(1)ϪN(2) 92.86(18)
The structure of the like isomer of the THF complex 7d
was determined by X-ray diffraction. Figure 9 shows the
cation.
The cyclopentadienyl moiety is again slightly slipped
such that the two carbon atoms trans to the NO ligand have
moved away from the rhenium atom. The nitrosyl and ni-
trile ligands are perfectly linear and the N(1)ϪRe(1)ϪN(2)
angle is in the typical range. This is somewhat in contrast
to the structure of (SRe,SC)-[CpRe(NO)(PPh3){NCCH-
(Ph)CH2CH3}]PF6 where a significantly bent nitrile ligand
and a widened N(1)ϪRe(1)ϪN(2) angle were observed.[32]
The refinement of the structure of 6e indicated some dis-
order which revealed the presence, in the crystal, of ca. 10%
of the like isomer. This is related to the predominating un-
like isomer through a reflection of the phosphane ligand at
a mirror plane which bisects the N(1)ϪRe(1)ϪN(2) angle
and passes through the centre of the cyclopentadienyl ring,
the rhenium atom and two carbon atoms of the thiophene
ring (Figure 8).
Figure 9. Structure of the cation of (SRe,SP/RRe,RP)-
[CpRe(NO){P(Ph)(Me)(2-C6H4OMe)}(THF)]BF4 (7d), hydrogen
atoms omitted for clarity. Space group P21/c; selected distances
[pm] and angles (°) (standard deviations in parentheses):
Re(1)ϪC(10) 228.9(8), Re(1)ϪC(11) 235.0(8), Re(1)ϪC(12)
230.6(8),
Re(1)ϪN(1) 174.9(7), Re(1)ϪO(3) 214.6(5), Re(1)ϪP(1) 238.64(18);
Re(1)ϪN(1)ϪO(1) 176.0(7), N(1)ϪRe(1)ϪO(3) 96.9(3),
P(1)ϪRe(1)ϪN(1) 90.8(2), P(1)ϪRe(1)ϪO(3) 87.60(14)
Treatment of the methyl complex 4d with HBF4 either in
a mixture of dichloromethane and acetonitrile or in pure
THF gave the cationic solvated complexes 6d and 7d with-
out any decomposition. Complex 7d could be isolated with
a de of 30% [Equation (5)].
Re(1)ϪC(13)
220.8(7),
Re(1)ϪC(14)
217.7(8),
As for the methyl complex 4d and the acetonitrile com-
plex 6e the cyclopentadienyl ligand is slipped, the difference
between the longest and the shortest ReϪC distances being
17 pm. Once again, the angle between the smallest ligands
THF and NO is widened [96.9(3)°]. Since this widening has
been observed for all NϪReϪX angles in all structures dis-
cussed herein, the origin of this distortion must be elec-
tronic in nature.
(5)
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Rhenium Complexes with Hemilabile Phosphane Ligands
FULL PAPER
Bruker AMX 400, Jeol JNM-LA 300, δ values relative to TMS.
13C NMR: Bruker AMX 400, Jeol JNM-LA 300, δ values relative
to TMS, assignments were routinely checked by DEPT procedures.
In some cases the 13C NMR signals of quaternary carbon atoms
were too weak to be detected. The 1H and 13C NMR signals of
the phenyl groups attached to phosphorus are very similar for all
compounds and have therefore been omitted from the lists of spec-
troscopic data. 31P NMR: Bruker AMX 400, Jeol JNM-LA 300, δ
values relative to 85% H3PO4. Elemental analyses: Analytical Lab-
All acetonitrile complexes were isolated in high yields as
yellow or brown solids. Except for [CpRe(NO){P(Ph)-
(Me)(CH2C4H7O)}(NCCH3)]BF4 (6c), the compounds are
stable in acetone and even in dichloromethane solution,
whereas 6c decomposes rapidly in both solvents.
The formation of the THF complex 7d deserves some
comment. It implies that the superior donor ability of THF
compared with the aryl methoxy group overrides the en-
tropy effect of the five-membered chelate ring.
Ϫ
oratory of the Institut für Anorganische Chemie. BF4 salts oc-
casionally give low carbon values due to trace formation of fluoro-
carbon compounds which escape detection. GC-MS: Fisons Instru-
ments Trio-1000. The following starting materials were obtained as
described in the literature: 2-(chloromethyl)thiophene,[35]
PPh2(CH2C4H7O) (1c),[13] PPh(2-C6H4OMe)2,[36] PPh(Me)(H)[37]
and [CpRe(CO)(NO)(NCCH3)]BF4 (2).[4] All other reagents were
used as purchased.
Discussion
It was the goal of this work to prepare diastereomeric
rhenium complexes which contain stereogenic centres both
at the metal and the phosphane ligand. Furthermore, the
phosphanes bear a donor function (e.g. oxygen or sulfur) to
allow intramolecular stabilisation of reactive intermediates.
Five such hemilabile phosphanes were investigated. Adapt-
ing published methods, the phosphanes could be coordi-
nated successfully to the rhenium complexes.
PPh2(CH2C4H3S) (1b): This compound has been obtained pre-
viously via Li reduction of Ph2PCl.[12] However, no yields or physi-
cal data were given. We found the following synthesis to be more
convenient. A solution of LiPPh2, prepared from PPh3 (8.00 g,
30.5 mmol) and excess lithium in THF (50 mL), was treated with
NH4Cl (1.45 g, 27.1 mmol) to quench LiPh. Freshly distilled 2-
(chloromethyl)thiophene (5.00 g, 37.7 mmol) was added dropwise
to the red solution at 20 °C. After stirring for 1 h at 20 °C, water
(15 mL) was added. The organic layer was separated, the aqueous
phase extracted four times with diethyl ether (50 mL) and the com-
bined organic phases dried with MgSO4. The solvent was removed
under vacuum and the colourless residue purified by recrystallis-
ation from methanol or by column chromatography over silica
(20 cm, petroleum ether/diethyl ether, 1:2). Yield 7.50 g (87%),
The phosphanes 1a and 1d which contain an ortho-anisyl
group as a potential donor did not give stable chelate com-
plexes. Although low temperature NMR experiments re-
vealed that at Ϫ50 °C the intramolecularly stabilised com-
plex [CpRe(NO){P(Ph)(Me)(2-C6H4OMe)}]BF4 (5d) is
formed, the ring opens at temperatures above Ϫ30 °C giving
rise to another cationic complex, probably the dichloro-
methane adduct which itself decomposes at temperatures
above Ϫ10 °C. The oxygen of the anisyl group is even less
efficient as a donor than THF. On the other hand, ring
closure was observed with the phosphanes 1b, 1c and 1e. In
these cases, neither THF nor acetone are strong enough
donors to break the ReϪO or ReϪS bonds, while aceto-
nitrile opens the rings irreversibly. As yet, no complete sep-
aration of the diastereoisomers could be achieved either
during the formation of the ring-closed complexes or by
fractional crystallisation (except for 4e, 5e and 7d). On the
other hand, once a sample enriched in one diastereomer is
employed, then the degree of enrichment is carried over to
the next step. This is in line with earlier observations that
substitution reactions at half-sandwich complexes of rhe-
nium proceed with retention of configuration.[33,34]
1
white solid, m.p. 50 °C. H NMR (400 MHz, CDCl3, 20 °C): δ ϭ
3.53 (s, br, 2 H, PCH2), 6.60 (m, 1 H, thiophene H), 6.74 (m, 1 H,
thiophene H), 6.96 (m, 1 H, thiophene H) ppm. 13C NMR
1
(100 MHz, CDCl3, 20 °C): δ ϭ 30.0 (d, JP,C ϭ 15 Hz, PCH2),
4
3
123.7 (d, JP,C ϭ 3 Hz, thiophene CH), 125.7 (d, JP,C ϭ 7 Hz,
4
thiophene CH), 126.8 (d, JP,C ϭ 1 Hz, thiophene CH), 139.8 (d,
2JP,C ϭ 11 Hz, PCH2C) ppm. 31P NMR (162 MHz, CDCl3, 20 °C):
δ ϭ Ϫ10.7 (s) ppm. C17H15PS (282.35): calcd. C 72.32, H 5.35, S
11.36; found C 72.10, H 5.54, S 10.87.
P(Me)(Ph)(2-C6H4OMe) (1d): The preparation of 1d starting from
PPh(2-C6H4OMe)2 was briefly mentioned in the literature, but no
details were given.[14] To a solution of sodium (4.00 g, 174 mmol)
in liquid ammonia (400 mL) was added PPh(2-C6H4OMe)2 (28.0 g,
86.9 mmol) and the mixture kept at Ϫ78 °C for 6 h. NH4Cl (4.50 g,
84.1 mmol) was then added followed by the dropwise addition of
MeI (6.00 mL, 13.7 g, 96.5 mmol). The ammonia was evaporated
overnight, the remaining pasty solid was washed twice with water
(50 mL) and distilled (kugelrohr, oven temperature 180 °C). The
colourless distillate solidified upon cooling to 20 °C. Yield 12.5 g
(63%) (ref.[14] 56%), white solid, m.p. 46 °C (ref.[38] 46Ϫ47 °C). The
Conclusions
Diastereomeric rhenium complexes containing a stereo-
genic metal centre and a chiral phosphane ligand are readily
accessible. Furthermore, if the phosphanes contain a second
donor atom, e.g. oxygen or sulfur, chelate ring closure can
occur. The stability of the chelate ring can be tuned by an
appropriate choice of donor function. Further modifi-
cations of the system are necessary to give access to dia-
stereomerically pure complexes.
NMR spectroscopic data were consistent with those given in ref.[38]
.
P(Ph)(Me)(CH2C4H3S) (1e): P(Ph)(Me)(H) (2.52 g, 20.3 mmol)
was dissolved in THF (10 mL) and deprotonated with BuLi
(8.5 mL 2.5 , 21.3 mmol) at Ϫ78 °C. The orange solution thus
obtained was slowly added to a cooled (Ϫ78 °C) solution of freshly
distilled 2-(chloromethyl)thiophene (2.69 g, 20.3 mmol) in THF
(10 mL). The mixture was warmed to 20 °C overnight, water
(3 mL) was added, the organic layer was separated and the aqueous
layer extracted three times with diethyl ether (20 mL). The com-
bined extracts were dried with MgSO4, the solvent removed and
the residue distilled under vacuum. Yield 3.26 g (73%), colourless
Experimental Section
All experiments were carried out in Schlenk tubes under nitrogen
using suitably purified solvents. IR: Bruker IFS 25. 1H NMR:
Eur. J. Inorg. Chem. 2004, 4859Ϫ4870
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4865

S. Dilsky, W. A. Schenk
FULL PAPER
1
oil, b.p. 100Ϫ113 °C/0.1 mbar. H NMR (400 MHz, C6D6, 20 °C):
20 °C): δ ϭ 2.6 (s) ppm. IR (CH2Cl2): ν˜ ϭ 2019 (CO), 1763 (NO)
δ ϭ 1.03 (d, JP,H ϭ 4.1 Hz, 3 H, PCH3), 2.88, 3.00 (ABX system, cmϪ1. C23H24BF4NO3PRe (666.43): calcd. C 41.45, H 3.63, N 2.10;
2
2JH,H ϭ 14.4, 2JP,H ϭ 3.6 Hz, 2 H, PCH2), 6.51 (m, 1 H, thiophene
H), 6.65 (m, 1 H, thiophene H), 6.73 (m, 1 H, thiophene H) ppm.
found C 41.34, H 3.88, N 1.90.
[CpRe(CO)(NO){P(Ph)(Me)(2-C6H4OMe)}]BF4 (3d): A solution of
acetonitrile complex 2 (1.00 g, 2.29 mmol) and phosphane 1d
(1.00 g, 4.34 mmol) in 2-butanone (20 mL) was heated to reflux for
30 h. Acetone (20 mL) was added, the mixture filtered through sil-
ica gel and the silica layer washed twice with acetone (10 mL). The
solvent was removed under vacuum and the oily residue dissolved
in THF (10 mL). Upon stirring, a yellow solid separated which was
collected by filtration and washed repeatedly with THF until the
washings remained almost colourless. Yield 0.88 g (62%), bright
13C NMR (100 MHz, C6D6, 20 °C): δ ϭ 10.7 (d, JP,C ϭ 17 Hz,
1
PCH3), 32.3 (d, 1JP,C ϭ 17 Hz, PCH2), 123.5 (d, 4JP,C ϭ 3 Hz, thio-
3
phene CH), 125.4 (d, JP,C ϭ 6 Hz, thiophene CH), 126.9 (d,
4JP,C ϭ 1 Hz, thiophene CH), 140.2 (d, JP,C ϭ 6 Hz, PCH2C). 31
P
2
NMR (162 MHz, C6D6, 20 °C): δ ϭ Ϫ29.9 (s) ppm. MS: m/z (%) ϭ
222 (1) [34S-Mϩ], 221 (3) [M ϩ H]ϩ, 220 (25) [Mϩ], 219 (11) [M Ϫ
H]ϩ, 97 (100) [CH2C4H3Sϩ]. C12H13PS (220.27).
[CpRe(CO)(NO)(PPh2(2-C6H4OMe))]BF4 (3a):
A solution of
acetonitrile complex 2 (500 mg, 1.14 mmol) and phosphane 1a yellow crystalline solid, m.p. 134 °C. Both diastereomers: 1H NMR
2
(500 mg, 1.71 mmol) in 2-butanone (10 mL) was heated to reflux
for 48 h. Acetone (10 mL) was added, the mixture filtered through
silica gel and the silica layer washed twice with acetone (10 mL).
The combined filtrate was evaporated to dryness and the residue
recrystallised from acetone/diethyl ether. Yield 665 mg (85%), yel-
(400 MHz, CD2Cl2, 20 °C): δ ϭ 2.46 (d, JP,H ϭ 10.4 Hz, 3 H,
PCH3), 2.52 (d, 2JP,H ϭ 10.4 Hz, 3 H, PCH3), 3.73 (s, 3 H, OCH3),
3.79 (s, 3 H, OCH3), 5.82 (s, 10 H, C5H5) ppm. 13C NMR
1
(100 MHz, CD2Cl2, 20 °C): δ ϭ 20.3 (d, JP,C ϭ 42 Hz, PCH3),
20.4 (d, 1JP,C ϭ 42 Hz, PCH3), 56.0 (s, OCH3), 56.2 (s, OCH3), 94.2
low-brown crystalline solid, m.p. 199 °C (dec.). 1H NMR (s, C5H5), 94.2 (s, C5H5), 195.2 (d, JP,C ϭ 9 Hz, CO), 195.8 (d,
2
(400 MHz, CD2Cl2, 20 °C): δ ϭ 3.74 (s, 3 H, OCH3), 5.79 (s, 5 H,
2JP,C ϭ 9 Hz, CO) ppm. 31P NMR (162 MHz, CD2Cl2, 20 °C): δ ϭ
C5H5) ppm. 13C NMR (100 MHz, CD2Cl2, 20 °C): δ ϭ 56.1 (s, Ϫ15.0 (s), Ϫ13.0 (s) ppm. IR (CH2Cl2): ν˜ ϭ 2021 (CO), 1763 (NO)
OCH3), 94.7 (s, C5H5), 194.9 (d, JP,C ϭ 10 Hz, CO) ppm. 31P cmϪ1. C20H20BF4NO3PRe (626.37): calcd. C 38.35, H 3.22, N 2.24;
2
NMR (162 MHz, CD2Cl2, 20 °C): δ ϭ 0.9 (s) ppm. IR (CH2Cl2): found C 38.60, H 3.35, N 2.22.
ν˜ ϭ 2029 (CO), 1763 (NO) cmϪ1. C25H22BF4NO3PRe (688.44):
calcd. C 43.62, H 3.22, N 2.03; found C 44.03, H 3.48, N 2.00.
[CpRe(CO)(NO){P(Ph)(Me)(CH2C4H3S)}]BF4 (3e): A solution of
acetonitrile complex 2 (600 mg, 1.37 mmol) and phosphane 1e
[CpRe(CO)(NO){PPh2(CH2C4H3S)}]BF4 (3b): A solution of aceto-
nitrile complex 2 (615 mg, 1.41 mmol) and phosphane 1b (500 mg,
1.77 mmol) in 2-butanone (15 mL) was heated to reflux for 48 h.
Acetone (10 mL) was added, the mixture filtered through silica gel
and the silica layer washed twice with acetone (8 mL). The com-
bined filtrate was evaporated to dryness and the residue recrystal-
(400 mg, 1.82 mmol) in 2-butanone (15 mL) was heated to reflux
for 4 h. Upon cooling, a yellow precipitate formed. Diethyl ether
(15 mL) was added and the solid was collected by filtration and
washed with THF. Yield 640 mg (76%), yellow crystalline solid,
m.p. 233 °C. Both diastereomers: 1H NMR (400 MHz, CD3CN, 20
2
2
°C): δ ϭ 2.19 (d, JP,H ϭ 10.4 Hz, 3 H, PCH3), 2.19 (d, JP,H
ϭ
2
lised twice from dichloromethane/diethyl ether and finally washed 10.4 Hz, 3 H, PCH3), 4.04, 4.13 (ABX system, JH,H ϭ 15.7,
with petroleum ether. Yield 840 mg (83%), yellow crystalline solid,
2JP,H ϭ 9.3 Hz, 2 H, PCH2), 4.07, 4.11 (ABX system, 2JH,H ϭ 15.4,
m.p. 106 °C (dec.). 1H NMR (400 MHz, CD2Cl2, 20 °C): δ ϭ 4.41, 2JP,H ϭ 10.0 Hz, 2 H, PCH2), 5.88 (d, JP,H ϭ 0.6 Hz, 5 H, C5H5),
3
4.51 (ABX system, 2JH,H ϭ 15.0 Hz, 2JP,H ϭ 10.4 Hz, 2 H, PCH2),
5.74 (s, 5 H, C5H5), 6.64 (m, 1 H, thiophene H), 6.87 (m, 1 H,
5.90 (d, JP,H ϭ 0.6 Hz, 5 H, C5H5), 6.80 (m, 2 H, thiophene H),
3
6.93 (m, 2 H, thiophene H), 7.27 (m, 2 H, thiophene H) ppm. 13C
thiophene H), 7.17 (m, 1 H, thiophene H) ppm. 13C NMR NMR (100 MHz, CD3CN, 20 °C): δ ϭ 16.1 (d, JP,C ϭ 40 Hz,
1
1
1
1
(100 MHz, CD2Cl2, 20 °C): δ ϭ 35.1 (d, JP,C ϭ 35 Hz, PCH2), PCH3), 16.2 (d, JP,C ϭ 40 Hz, PCH3), 35.2 (d, JP,C ϭ 34 Hz,
4
94.4 (s, C5H5), 126.9 (d, JP,C ϭ 4 Hz, thiophene CH), 127.7 (d,
PCH2), 35.4 (d, 1JP,C ϭ 34 Hz, PCH2), 94.7 (d, 2JP,C ϭ 1 Hz. C5H5),
3
2
4JP,C ϭ 3 Hz, thiophene CH), 129.7 (d, JP,C ϭ 7 Hz, thiophene 94.8 (d, JP,C ϭ 1 Hz. C5H5), 127.1 (d, 4JP,C ϭ 4 Hz, thiophene
2
2
CH), 132.5 (d, JP,C ϭ 6 Hz, PCH2C), 194.7 (d, JP,C ϭ 9 Hz, CO) CH), 127.1 (d, 4JP,C ϭ 4 Hz, thiophene CH), 128.3 (d, 4JP,C
ppm. 31P NMR (162 MHz, CD2Cl2, 20 °C): δ ϭ 14.6 (s) ppm. IR
4 Hz, thiophene CH), 128.3 (d, 4JP,C ϭ 4 Hz, thiophene CH), 129.7
(CH2Cl2): ν˜ 2016 (CO), 1767 (NO) (d, 3JP,C ϭ 7 Hz, thiophene CH), 129.8 (d, 3JP,C ϭ 7 Hz, thiophene
cmϪ1
C23H20BF4NO2PReS·(C2H5)2O (715.53): calcd. C 41.97, H 3.52, N CH), 134.1 (d, JP,C ϭ 10 Hz, PCH2C), 134.2 (d, JP,C ϭ 10 Hz,
ϭ
ϭ
.
2
2
2
2
1.96, S 4.48; found C 41.47, H 3.30, N 1.96, S 4.57.
PCH2C), 195.9 (d, JP,C ϭ 7 Hz, CO), 195.9 (d, JP,C ϭ 7 Hz, CO)
ppm. 31P NMR (162 MHz, CD3CN, 20 °C): δ ϭ Ϫ6.4 (s), Ϫ5.5 (s)
ppm. IR (Nujol): ν˜
[CpRe(CO)(NO){PPh2(CH2C4H7O)}]BF4 (3c): A solution of aceto-
nitrile complex 2 (1.00 g, 2.29 mmol) and phosphane 1c (0.88 g,
3.26 mmol) in 2-butanone (20 mL) was heated to reflux for 48 h.
Acetone (20 mL) was added, the mixture filtered through silica gel
and the silica layer washed twice with acetone (10 mL). The com-
bined filtrate was evaporated to dryness and the residue washed
with diethyl ether. Yield 1.45 g (95%), yellow crystalline solid, m.p.
156 °C (dec.). Both diastereomers: 1H NMR (400 MHz, CD2Cl2,
ϭ
2016 (CO), 1763 (NO) cmϪ1
.
C18H18BF4NO2PReS (616.40): calcd. C 35.07, H 2.94, N 2.27, S
5.20; found C 34.83, H 2.92, N 2.30, S 5.09.
[CpRe(NO){PPh2(2-C6H4OMe)}(CH3)] (4a): To a suspension of
carbonyl complex 3a (300 mg, 0.44 mmol) in THF (15 mL) was
added NaBH4 (50 mg, 1.32 mmol). The colour of the mixture
changed from brown to red and a gas was evolved. After 2 h, the
solution was evaporated to dryness, the residue dissolved in ben-
20 °C): δ ϭ 1.60Ϫ2.11 (m, 8 H, CH2CH2), 2.92Ϫ3.19 (m, 4 H,
3
PCH2), 3.53Ϫ3.85 (m, 6 H, CH2OCH), 5.77 (d, JP,H ϭ 0.4 Hz, 5 zene (15 mL), filtered through silica gel and the silica washed with
3
H, C5H5), 5.78 (d, JP,H ϭ 0.4 Hz, 5 H, C5H5) ppm. 13C NMR benzene. The clear, orange filtrate was evaporated to 1 mL and the
(100 MHz, CD2Cl2, 20 °C): δ ϭ 25.1 (s, CH2), 25.2 (s, CH2), 33.5
product precipitated upon addition of petroleum ether and storing
3
3
(d, JP,C ϭ 12 Hz, CH2), 33.6 (d, JP,C ϭ 12 Hz, CH2), 37.9 (d, overnight at Ϫ30 °C. Yield 220 mg (87%), orange crystalline solid,
1
1
1JP,C ϭ 37 Hz, PCH2), 38.3 (d, JP,C ϭ 37 Hz, PCH2), 68.3 (s, m.p. 55 °C (dec.). H NMR (400 MHz, C6D6, 20 °C): δ ϭ 1.45 (d,
OCH2), 68.4 (s, OCH2), 74.2 (d, JP,C ϭ 3 Hz, OCH), 74.5 (d,
3JP,H ϭ 6.4 Hz, 3 H, ReCH3), 3.05 (s, 3 H, OCH3), 4.61 (s, 5 H,
C5H5) ppm. 13C NMR (100 MHz, C6D6, 20 °C): δ ϭ Ϫ35.7 (d,
2
2
2JP,C ϭ 3 Hz, OCH), 94.3 (s, C5H5), 195.4 (d, JP,C ϭ 8 Hz, CO),
195.5 (d, JP,C ϭ 8 Hz, CO) ppm. 31P NMR (162 MHz, CD2Cl2, 2JP,C ϭ 7 Hz, ReCH3), 55.0 (s, OCH3), 89.6 (d, 2JP,C ϭ 2 Hz, C5H5)
2
4866
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 4859Ϫ4870

Rhenium Complexes with Hemilabile Phosphane Ligands
FULL PAPER
ppm. 31P NMR (162 MHz, C6D6, 20 °C): δ ϭ 21.4 (s) ppm. IR ReCH3), 15.9 (d, JP,C ϭ 35 Hz, PCH3), 16.5 (d, JP,C ϭ 35 Hz,
1
1
(THF): ν˜ ϭ 1637 (NO) cmϪ1. C25H25NO2PRe (588.66): calcd. C PCH3), 54.7 (s, OCH3), 55.0 (s, OCH3), 88.5 (d, JP,C ϭ 2 Hz,
2
2
51.01, H 4.28, N 2.38; found C 50.86, H 4.37, N 2.27.
C5H5), 88.7 (d, JP,C ϭ 2 Hz, C5H5]) ppm. 31P NMR (162 MHz,
C6D6, 20 °C): δ ϭ Ϫ1.2 (s), 0.5 (s) ppm. IR (THF): ν˜ ϭ 1636 (NO)
cmϪ1. C20H23NO2PRe (526.59): calcd. C 45.62, H 4.40, N 2.66;
found C 45.95, H 4.50, N 2.62.
[CpRe(NO){PPh2(CH2C4H3S)}(CH3)] (4b): To a suspension of car-
bonyl complex 3b (270 mg, 0.40 mmol) in THF (15 mL) was added
NaBH4 (50 mg, 1.32 mmol). The colour of the mixture changed
from brown to red and a gas was evolved. After 2 h, the solution
was evaporated to dryness, the residue dissolved in benzene
(20 mL), filtered through silica gel and celite and the filter aid
washed with benzene. The solvent was removed under vacuum and
the residue dissolved in boiling hexane (40 mL). The solution was
filtered hot over celite and the solvents evaporated to 10 mL. The
initial crystallisation was completed by storing the mixture over-
night at Ϫ30 °C. Yield 174 mg (76%), orange crystalline solid, m.p.
86 °C (dec.). 1H NMR (400 MHz, C6D6, 20 °C): δ ϭ 1.42 (d,
3JP,H ϭ 5.8 Hz, 3 H, ReCH3] 3.95, 4.01 (ABX system, 2JH,H ϭ 15.0,
2JP,H ϭ 9.0 Hz, 2 H, PCH2), 4.50 (s, 5 H, C5H5), 6.46 (m, 1 H,
thiophene H), 6.54 (m, 1 H, thiophene H), 6.64 (m, 1 H, thiophene
H) ppm. 13C NMR (100 MHz, C6D6, 20 °C): δ ϭ Ϫ38.7 (d, 2JP,C ϭ
8 Hz, ReCH3), 32.9 (d, 1JP,C ϭ 29 Hz, PCH2), 89.0 (d, 2JP,C ϭ 2 Hz.
[CpRe(NO){P(Ph)(Me)(CH2C4H3S)}(CH3)] (4e): To a suspension
of carbonyl complex 3e (350 mg, 0.57 mmol) in THF (15 mL) was
added NaBH4 (65 mg, 1.72 mmol). The mixture turned red and a
gas was evolved. After 2 h, the reaction was worked up as described
for 4a. Yield 237 mg (81%), orange crystalline powder, m.p. 67 °C.
Recrystallisation from hot petroleum ether gave a sample enriched
in one diastereomer. Major (68%) diastereomer: 1H NMR
(400 MHz, C6D6, 20 °C): δ ϭ 1.12 (d, 3JP,H ϭ 6.2 Hz, 3 H, ReCH3),
2
1.44 (d, JP,H ϭ 8.6 Hz, 3 H, PCH3), 3.47, 3.61 (ABX system,
2JH,H ϭ 15.0, 2JP,H ϭ 8.6 Hz, 2 H, PCH2), 4.52 (s, 5 H, C5H5), 6.40
(m, 1 H, thiophene H), 6.57 (m, 1 H, thiophene H), 6.64 (m, 1 H,
thiophene H) ppm. 13C NMR (100 MHz, C6D6, 20 °C): δ ϭ Ϫ39.3
2
1
(d, JP,C ϭ 7 Hz, ReCH3), 15.1 (d, JP,C ϭ 36 Hz, PCH3), 33.7 (d,
1JP,C ϭ 30 Hz, PCH2), 87.9 (d, JP,C ϭ 2 Hz. C5H5), 124.2 (d,
2
4
4
4
4JP,C ϭ 3 Hz, thiophene CH), 126.8 (d, JP,C ϭ 2 Hz, thiophene
C5H5), 124.4 (d, JP,C ϭ 3 Hz, thiophene CH), 126.8 (d, JP,C
ϭ
2
2 Hz, thiophene CH), 136.7 (d, JP,C ϭ 6 Hz, PCH2C) ppm. 31P
NMR (162 MHz, C6D6, 20 °C): δ ϭ 19.7 (s) ppm. IR (THF): ν˜ ϭ
1634 (NO) cmϪ1. C23H23NOPReS (578.69): calcd. C 47.74, H 4.01,
N 2.42, S 5.54; found C 48.17, H 4.18, N 2.32, S 5.60.
CH), 127.5 (d, 3JP,C ϭ 5 Hz, thiophene CH), 137.2 (d, 2JP,C ϭ 8 Hz,
PCH2C) ppm. 31P NMR (162 MHz, C6D6, 20 °C): δ ϭ Ϫ0.9 (s)
ppm. Minor (32%) diastereomer: 1H NMR (400 MHz, C6D6, 20
3
2
°C): δ ϭ 1.22 (d, JP,H ϭ 6.1 Hz, 3 H, ReCH3), 1.40 (d, JP,H
ϭ
8.6 Hz, 3 H, PCH3), 3.67, 3.69 (ABX system, 2JH,H ϭ 15.7, 2JP,H ϭ
7.5 Hz, 2 H, PCH2), 4.54 (s, 5 H, C5H5), 6.23 (m, 1 H, thiophene
H), 6.53 (m, 1 H, thiophene H), 6.62 (m, 1 H, thiophene H) ppm.
[CpRe(NO){PPh2(CH2C4H7O)}(CH3)] (4c): To a solution of car-
bonyl complex 3c (390 mg, 0.59 mmol) in THF (20 mL) was added
NaBH4 (70 mg, 1.85 mmol) at Ϫ78 °C. After 30 min at that tem-
perature, the mixture was allowed to warm to 20 °C which was
accompanied by gas evolution. The mixture was filtered through
silica gel and the silica washed with THF. After evaporation of the
solvent, the residue was dissolved in benzene (20 mL), the solution
filtered through celite and the solvents evaporated again. The resi-
due was finally recrystallised at Ϫ78 °C from toluene (2 mL) and
hexane (10 mL). Yield 265 mg (80%), orange powder, m.p. 40 °C.
Both diastereomers: 1H NMR (400 MHz, C6D6, 20 °C): δ ϭ
0.66Ϫ0.97 (m, 2 H, CH2), 1.03Ϫ1.44 (m, 4 H, CH2), 1.49 (d,
3JP,H ϭ 5.5 Hz, 3 H, ReCH3), 1.52 (d, 3JP,H ϭ 5.6 Hz, 3 H, ReCH3),
2.53Ϫ2.88 (m, 2 H, CH2), 3.22Ϫ3.64 (m, 4 H, CH2), 4.13Ϫ4.41
(m, 2 H, CH), 4.49 (s, 5 H, C5H5), 4.61 (s, 5 H, C5H5) ppm. 13C
13C NMR (100 MHz, C6D6, 20 °C): δ ϭ Ϫ40.2 (d, JP,C ϭ 7 Hz,
2
1
1
ReCH3), 11.2 (d, JP,C ϭ 32 Hz, PCH3), 33.2 (d, JP,C ϭ 30 Hz,
PCH2), 88.0 (d, JP,C ϭ 2 Hz. C5H5), 124.3 (d, JP,C ϭ 3 Hz, thio-
2
4
4
phene CH), 126.7 (d, JP,C ϭ 3 Hz, thiophene CH), 127.3 (d,
2
3JP,C ϭ 5 Hz, thiophene CH), 136.9 (d, JP,C ϭ 10 Hz, PCH2C)
ppm. 31P NMR (162 MHz, C6D6, 20 °C): δ ϭ Ϫ4.0 (s) ppm. Both
diastereomers: IR (THF): ν˜ ϭ 1631 (NO) cmϪ1. C18H21NOPReS
(516.62): calcd. C 41.85, H 4.10, N 2.71, S 6.21; found C 42.00, H
4.09, N 2.67, S 5.84.
Chelate Complexes 5b؊e: At Ϫ78 °C, HBF4 in diethyl ether (150
µL, ca. 1.50 mmol) was added to a solution of the respective methyl
complex (0.38 mmol) in dichloromethane (10 mL). Gas evolution
and a change of colour from red to brown was observed. After 1 h,
the temperature was raised to 20 °C and the solvents were evapo-
rated to 2 mL. The product, which was precipitated by addition of
diethyl ether, was filtered off and washed with diethyl ether and
petroleum ether.
2
NMR (100 MHz, C6D6, 20 °C): δ ϭ Ϫ39.8 (d, JP,C ϭ 7 Hz,
2
ReCH3), Ϫ38.6 (d, JP,C ϭ 7 Hz, ReCH3), 25.9 (s, CH2), 26.2 (s,
3
3
CH2), 32.7 (d, JP,C ϭ 3 Hz, CH2), 32.9 (d, JP,C ϭ 8 Hz, CH2),
1
1
37.5 (d, JP,C ϭ 31 Hz, PCH2), 39.2 (d, JP,C ϭ 35 Hz, PCH2), 67.0
2
(s, OCH2), 67.4 (s, OCH2), 76.3 (d, JP,C ϭ 7 Hz, OCH), 77.0 (d,
2JP,C ϭ 2 Hz, OCH), 89.2 (d, 2JP,C ϭ 2 Hz. C5H5), 89.3 (d, JP,C
ϭ
2
2 Hz. C5H5) ppm. 31P NMR (162 MHz, C6D6, 20 °C): δ ϭ 8.1 (s),
11.1 (s) ppm. IR (THF): ν˜ ϭ 1632 (NO) cmϪ1. C23H27NO2PRe
(588.65): calcd. C 48.75, H 4.80, N 2.47; found C 48.56, H 4.70,
N 2.36.
[CpRe(NO)(κPPh2(CH2C4H3κS))]BF4 (5b): Yield 212 mg (86%),
yellow crystalline solid, m.p. 218 °C (dec.). 1H NMR (400 MHz,
2
CD2Cl2, 20 °C): δ ϭ 3.64, 4.01 (ABMX system, JH,H ϭ 16.2,
2JP,H ϭ 11.2, 4JH,H ϭ 1.2 Hz, 2 H, PCH2), 5.49 (s, 5 H, C5H5) ppm.
1
13C NMR (100 MHz, CD2Cl2, 20 °C): δ ϭ 27.7 (d, JP,C ϭ 32 Hz,
[CpRe(NO){P(Ph)(Me)(2-C6H4OMe})(CH3)] (4d): To a suspension
of carbonyl complex 3d (500 mg, 0.80 mmol) in THF (15 mL) was
added NaBH4 (95 mg, 2.50 mmol). The colour of the mixture
changed from brown to red and a gas was evolved. After 2 h, the
reaction was worked up as described for 4b. Yield 344 mg (82%),
orange-red crystalline powder, m.p. 206 °C (dec.). Both dia-
stereomers: 1H NMR (400 MHz, C6D6, 20 °C): δ ϭ 1.25 (d, 3JP,H ϭ
2
4
PCH2), 91.8 (d, JP,C ϭ 1 Hz, C5H5), 132.0 (d, JP,C ϭ 3 Hz, thio-
4
phene CH), 133.2 (d, JP,C ϭ 3 Hz, thiophene CH), 134.9 (d,
3JP,C ϭ 3 Hz, thiophene CH), 161.4 (d, 2JP,C ϭ 3 Hz, PCH2C) ppm.
31P NMR (162 MHz, CD2Cl2, 20 °C): δ ϭ 34.5 (s) ppm. IR
(CH2Cl2): ν˜ ϭ 1722 (NO) cmϪ1. C22H20BF4NOPReS (650.46):
calcd. C 40.62, H 3.10, N 2.15, S 4.93; found C 39.67, H 3.27, N
2.02, S 4.68.
3
6.2 Hz, 3 H, ReCH3), 1.26 (d, JP,H ϭ 6.4 Hz, 3 H, ReCH3), 1.97
2
2
(d, JP,H ϭ 8.8 Hz, 3 H, PCH3), 1.99 (d, JP,H ϭ 9.1 Hz, 3 H, [CpRe(NO){κPPh2(CH2C4H7κO)}]BF4 (5c): Yield 243 mg (99%),
1
PCH3), 2.89 (s, 3 H, OCH3), 3.02 (s, 3 H, OCH3), 4.65 (s, 5 H, brownish solid, m.p. 182 °C (dec.). Both diastereomers: H NMR
C5H5), 4.71 (s, 5 H, C5H5) ppm. 13C NMR (100 MHz, C6D6, 20 (400 MHz, CD2Cl2, 20 °C): δ ϭ 1.90Ϫ2.04 (m, 1 H, CH2),
2
2
°C): δ ϭ Ϫ38.7 (d, JP,C ϭ 6 Hz, ReCH3), Ϫ38.7 (d, JP,C ϭ 6 Hz,
2.05Ϫ2.49 (m, 9 H, CH2), 2.73Ϫ2.89 (m, 2 H, CH2), 4.06Ϫ4.18
Eur. J. Inorg. Chem. 2004, 4859Ϫ4870
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4867

S. Dilsky, W. A. Schenk
FULL PAPER
(m, 1 H, CH), 4.27Ϫ4.33 (m, 1 H, CH), 4.35Ϫ4.54 (m, 4 H, PCH2), [CpRe(NO){P(Ph)(Me)(CH2C4H3S)}(NCCH3)]BF4 (6e): Yield
5.49 (s, 5 H, C5H5), 5.52 (s, 5 H, C5H5) ppm. 13C NMR (100 MHz, 117 mg (93%), dark yellow crystalline solid, m.p. 114 °C. Both dia-
3
CD2Cl2, 20 °C): δ ϭ 28.2 (s, CH2), 28.5 (s, CH2), 29.7 (d, JP,C
ϭ
stereomers: 1H NMR (400 MHz, CD2Cl2, 20 °C): δ ϭ 2.04 (d,
3
1
2
11 Hz, CH2), 31.6 (d, JP,C ϭ 10 Hz, CH2), 31.8 (d, JP,C ϭ 28 Hz,
2JP,H ϭ 9.5 Hz, 3 H, PCH3), 2.04 (d, JP,H ϭ 9.6 Hz, 3 H, PCH3),
1
5
5
PCH2), 35.8 (d, JP,C ϭ 27 Hz, PCH2), 88.7 (s, OCH2), 89.7 (s, 2.42 (d, JP,H ϭ 1.3 Hz, 3 H, NCCH3), 2.80 (d, JP,H ϭ 1.3 Hz, 3
OCH2), 90.8 (d, 2JP,C ϭ 2 Hz, C5H5), 91.1 (d, 2JP,C ϭ 2 Hz, C5H5), H, NCCH3), 3.95 (m, 4 H, PCH2), 5.44 (s, 5 H, C5H5), 5.53 (s, 5
95.8 (s, OCH), 97.9 (s, OCH) ppm. 31P NMR (162 MHz, CD2Cl2,
20 °C): δ ϭ 35.3 (s), 37.5 (s) ppm. IR (CH2Cl2): ν˜ ϭ 1690 (NO)
H, C5H5), 6.74 (m, 1 H, thiophene H), 6.82 (m, 1 H, thiophene H),
6.90 (m, 1 H, thiophene H), 6.96 (m, 1 H, thiophene H), 7.15 (m,
cmϪ1. C22H24BF4NO2PRe (638.42): calcd. C 41.39, H 3.79, N 2.19; 1 H, thiophene H), 7.23 (m, 1 H, thiophene H) ppm. 13C NMR
found C 41.09, H 3.93, N 1.97.
(100 MHz, CD2Cl2, 20 °C): δ ϭ 4.3 (s, NCCH3), 5.1 (s, NCCH3),
1
1
13.3 (d, JP,C ϭ 37 Hz, PCH3), 13.5 (d, JP,C ϭ 37 Hz, PCH3), 33.2
[CpRe(NO){κP(Ph)(Me)(CH2C4H3κS)}]BF4 (5e): Yield 204 mg
(91%), yellow crystalline powder, m.p. 69 °C (dec.). Careful extrac-
tion with THF gave a sample enriched in one diastereomer. Major
diastereomer: 1H NMR (400 MHz, CD2Cl2, 20 °C): δ ϭ 2.19 (d,
2JP,H ϭ 10.2 Hz, 3 H, PCH3), 3.06Ϫ3.63 (m, 2 H, PCH2), 5.45 (d,
3JP,H ϭ 0.3 Hz, 5 H, C5H5). 13C NMR (100 MHz, CD2Cl2, 20 °C):
1
1
(d, JP,C ϭ 31 Hz, PCH2), 33.8 (d, JP,C ϭ 35 Hz, PCH2), 91.1 (d,
2JP,C ϭ 1 Hz, C5H5), 91.4 (d, 2JP,C ϭ 1 Hz, C5H5), 125.7 (d, 4JP,C ϭ
4 Hz, thiophene CH), 125.9 (d, 4JP,C ϭ 4 Hz, thiophene CH), 127.5
(d, 4JP,C ϭ 3 Hz, thiophene CH), 127.7 (d, 4JP,C ϭ 3 Hz, thiophene
CH), 128.7 (d, 3JP,C ϭ 7 Hz, thiophene CH), 128.7 (d, 3JP,C ϭ 7 Hz,
thiophene CH), 134.2 (d, 2JP,C ϭ 10 Hz, PCH2C), 134.5 (d, 2JP,C ϭ
8 Hz, PCH2C), 139.7 (s, NCCH3), 140.8 (s, NCCH3) ppm. 31P
NMR (162 MHz, CD2Cl2, 20 °C): δ ϭ Ϫ11.8 (s), Ϫ6.9 (s) ppm.
IR (CH2Cl2): ν˜ ϭ 1699 (NO) cmϪ1. C19H21BF4N2OPReS (629.44):
calcd. C 36.26, H 3.36, N 4.45, S 5.09; found. C 36.16, H 3.50, N
4.29, S 4.93.
1
1
δ ϭ 14.7 (d, JP,C ϭ 39 Hz, PCH3), 26.3 (d, JP,C ϭ 32 Hz, PCH2),
2
91.6 (s, C5H5), 161.5 (d, JP,C ϭ 2 Hz, PCH2C). 31P NMR
(162 MHz, CD2Cl2, 20 °C): δ ϭ 11.3 (s) ppm. Minor diastereomer:
1H NMR (400 MHz, CD2Cl2, 20 °C): δ ϭ 2.21 (d, 2JP,H ϭ 10.0 Hz,
3 H, PCH3), 3.06Ϫ3.63 (m, 2 H, PCH2), 5.83 (d, 3JP,H ϭ 0.2 Hz, 5
H, C5H5) ppm. 13C NMR (100 MHz, CD2Cl2, 20 °C): δ ϭ 18.1 (d,
1JP,C ϭ 36 Hz, PCH3), 26.5 (d, JP,C ϭ 33 Hz, PCH2), 90.7 (s,
1
[CpRe(NO){P(Ph)(Me)(2-C6H4OMe)}(NCCH3)]BF4 (6d): To
a
C5H5), 163.0 (s, PCH2C) ppm. 31P NMR (162 MHz, CD2Cl2, 20
°C): δ ϭ 15.6 (s) ppm. Both diastereomers: IR (CH2Cl2): ν˜ ϭ 1718
(NO) cmϪ1. C17H18BF4NOPReS (588.39): calcd. C 34.70, H 3.08,
N 2.38, S 5.45; found C 34.62, H 3.36, N 2.28, S 5.19.
cold (Ϫ78 °C) solution of methyl complex 4d (65 mg, 0.12 mmol)
in dichloromethane (3 mL) and acetonitrile (1 mL) was added eth-
ereal HBF4 (25 µL, ca. 0.25 mmol). The mixture was kept cold for
1 h and was then allowed to warm to room temperature. The sol-
vent was removed under vacuum, the residue dissolved in dichloro-
methane (1 mL) and the product precipitated by the addition of
diethyl ether. Yield 78 mg (99%), yellow crystalline solid, m.p. 183
°C (dec.). Both diastereomers: 1H NMR (400 MHz, CD2Cl2, 20
Acetonitrile Complexes 6b؊e: A solution of the respective chelate
complex (0.20 mmol) in acetonitrile (5 mL) was kept for 24 h at
20 °C. The solvents were evaporated to dryness and the product
recrystallised from dichloromethane/diethyl ether.
2
2
°C): δ ϭ 2.24 (d, JP,H ϭ 9.5 Hz, 3 H, PCH3), 2.36 (d, JP,H
ϭ
5
9.8 Hz, 3 H, PCH3), 2.42 (d, JP,H ϭ 1.5 Hz, 3 H, NCCH3), 2.63
[CpRe(NO){PPh2(CH2C4H3S)}(NCCH3)]BF4 (6b): Yield 125 mg
90%), yellow crystalline solid, m.p. 232 °C (dec.). 1H NMR
(400 MHz, CD2Cl2, 20 °C): δ ϭ 2.63 (d, JP,H ϭ 1.2 Hz, 3 H,
5
(d, JP,H ϭ 1.4 Hz, 3 H, NCCH3), 3.59 (s, 3 H, OCH3), 3.67 (s, 3
H, OCH3), 5.57 (s, 5 H, C5H5), 5.60 (s, 5 H, C5H5) ppm. 13C NMR
(100 MHz, CD2Cl2, 20 °C): δ ϭ 4.0 (s, NCCH3), 4.5 (s, NCCH3),
5
2
2
NCCH3), 4.31, 4.46 (ABX system, JH,H ϭ 15.1, JP,H ϭ 10.1 Hz,
2 H, PCH2), 5.40 (s, 5 H, C5H5), 6.72 (m, 1 H, thiophene H), 6.87
1
1
16.8 (d, JP,C ϭ 38 Hz, PCH3), 18.9 (d, JP,C ϭ 39 Hz, PCH3), 56.0
(s, OCH3), 56.0 (s, OCH3), 91.3 (d, JP,C ϭ 1 Hz, C5H5), 91.7 (d,
2
(m, 1 H, thiophene H), 7.13 (m, 1 H, thiophene H) ppm. 13C NMR
2JP,C ϭ 1 Hz, C5H5), 139.5 (s, NCCH3), 140.2 (s, NCCH3) ppm.
31P NMR (162 MHz, CD2Cl2, 20 °C): δ ϭ Ϫ12.1 (s), Ϫ11.2 (s)
ppm. IR (CH2Cl2): ν˜ ϭ 1705 (NO) cmϪ1. C21H23BF4N2O2PRe
(639.41): calcd. C 39.45, H 3.63, N 4.38; found C 38.26, H 3.95,
N 4.06.
1
(100 MHz, CD2Cl2, 20 °C): δ ϭ 4.9 (s, NCCH3), 33.0 (d, JP,C
ϭ
4
33 Hz, PCH2), 91.9 (s, C5H5), 126.0 (d, JP,C ϭ 4 Hz, thiophene
CH), 127.4 (d, 4JP,C ϭ 3 Hz, thiophene CH), 129.4 (d, 3JP,C ϭ 7 Hz,
thiophene CH), 134.5 (d, 2JP,C ϭ 4 Hz, PCH2C), 141.3 (s, NCCH3)
ppm. 31P NMR (162 MHz, CD2Cl2, 20 °C): δ ϭ 9.2 (s) ppm. IR
(CH2Cl2): ν˜ ϭ 1705 (NO) cmϪ1. C24H23BF4N2OPReS (691.51):
calcd. C 41.69, H 3.35, N 4.05, S 4.64; found C 40.65, H 3.54, N
3.67, S 4.48.
[CpRe(NO){P(Ph)(Me)(2-C6H4OMe)}(THF)]BF4 (7d): To a cold
(Ϫ78 °C) solution of methyl complex 4d (210 mg, 0.40 mmol) in
THF (20 mL) was added ethereal HBF4 (100 µL, ca. 1.0 mmol).
The mixture was kept cold for 1 h and was then warmed to room
temperature. The solvents were evaporated to 10 mL and the prod-
[CpRe(NO){PPh2(CH2C4H7O)}(NCCH3)]BF4 (6c): Yield 112 mg
(82%), yellow-brown solid, m.p. 139 °C (dec.). Both diastereomers:
1H NMR (400 MHz, [D6]acetone, 20 °C): δ ϭ 1.66Ϫ2.17 (m, 6 H, uct precipitated upon the addition of diethyl ether. Yield 235 mg
5
5
CH2), 2.89 (d, JP,H ϭ 1.2 Hz, 3 H, NCCH3), 2.95 (d, JP,H
ϭ
(88%) pink powder, m.p. 88 °C (dec.). Major diastereomer: 1H
1.2 Hz, 3 H, NCCH3), 2.86Ϫ3.10 (m, 4 H, PCH2), 3.14Ϫ3.29 (m, NMR (400 MHz, [D6]acetone, 20 °C): δ ϭ 1.72Ϫ1.82 (m, 4 H,
2
2 H, CH2), 3.50Ϫ3.58 (m, 2 H, CH2), 3.65Ϫ3.75 (m, 2 H, CH2), CH2), 2.41 (d, JP,H ϭ 9.4 Hz, 3 H, PCH3), 3.56Ϫ3.65 (m, 4 H,
3.95Ϫ4.05 (m, 2 H, CH), 5.70 (s, 5 H, C5H5), 5.75 (s, 5 H, C5H5) OCH2), 3.63 (s, 3 H, OCH3), 5.97 (s, 5 H, C5H5) ppm. 13C NMR
ppm. 13C NMR (100 MHz, [D6]acetone, 20 °C): δ ϭ 4.5 (s, (100 MHz, [D6]acetone, 20 °C): δ ϭ 18.4 (d, 1JP,C ϭ 39 Hz, PCH3),
NCCH3), 4.5 (s, NCCH3), 25.9 (s, CH2), 25.9 (s, CH2), 33.6 (d,
26.1 (s, CH2), 56.0 (s, OCH3), 68.0 (s, OCH2), 92.5 (d, 2JP,C ϭ 1 Hz,
3JP,C ϭ 10 Hz, CH2), 33.7 (d, 3JP,C ϭ 10 Hz, CH2), 37.0 (d, 1JP,C ϭ C5H5) ppm. 31P NMR (162 MHz, [D6]acetone, 20 °C): δ ϭ Ϫ6.2
1
34 Hz, PCH2), 37.4 (d, JP,C ϭ 35 Hz, PCH2), 68.1 (s, OCH2), 68.2 (s) ppm. Minor diastereomer: 1H NMR (400 MHz, [D6]acetone, 20
2
2
(s, OCH2), 75.9 (s, OCH), 76.4 (s, OCH), 92.7 (d, JP,C ϭ 1 Hz, °C): δ ϭ 1.55Ϫ1.62 (m, 4 H, CH2), 2.47 (d, JP,H ϭ 10.1 Hz, 3 H,
2
C5H5), 92.8 (d, JP,C ϭ 1 Hz, C5H5) ppm, NCCH3 not observed.
PCH3), 3.35Ϫ3.42 (m, 4 H, OCH2), 3.72 (s, 3 H, OCH3), 5.90 (s 5
31P NMR (162 MHz, [D6]acetone, 20 °C): δ ϭ 1.9 (s), 2.7 (s) ppm.
H, C5H5) ppm. 13C NMR (100 MHz, [D6]acetone, 20 °C): δ ϭ 16.3
IR (CH3CN): ν˜ ϭ 1702 (NO) cmϪ1. C24H27BF4N2O2PRe (679.48): (d, JP,C ϭ 38 Hz, PCH3), 27.4 (s, CH2), 56.1 (s, OCH3), 71.1 (s,
1
2
calcd. C 42.42, H 4.01, N 4.12; found. C 41.96, H 4.03, N 3.97.
OCH2), 93.2 (d, JP,C ϭ 1 Hz, C5H5) ppm. 31P NMR (162 MHz,
4868
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 4859Ϫ4870

Rhenium Complexes with Hemilabile Phosphane Ligands
FULL PAPER
Table 1. Details of the structure determinations of compounds 1b·BH3, 3a, 3b, 3dϪAlF4, 4d, 6e and 7d·CH2Cl2
1b·BH3
3a
3b
3dϪAlF4
4d
6e
7d·CH2Cl2
Empirical formula
Formula mass
C14H18BOP
244.06
C25H22BF4NO3Pre C23H20BF4NO2PReS C20H20AlF4NO3PRe C20H23NO2PRe
C19H21BF4N2OPReS C24H30BClF4NO3PRe
688.42
678.44
642.52
526.56
629.42
755.40
Crystal colour/habit colourless plate
yellow block
monoclinic
P21/c
16.1437(13)
8.9379(7)
19.4659(16)
90
yellow block
triclinic
P1
yellow block
monoclinic
P21/n
11.1876(7)
13.8896(9)
14.3243(9)
90
red block
triclinic
P1
yellow plate
monoclinic
P21/c
11.1343(10)
9.7129(9)
20.4158(19)
90
red prism
monoclinic
P21/c
9.920(3)
18.071(5)
16.858(5)
90
Crystal system
Space group
orthorhombic
Pna21
10.5951(8)
9.6350(8)
15.7090(12)
90
¯
¯
˚
a (A)
9.954(2)
10.401(2)
12.264(3)
79.742(3)
75.758(3)
77.036(3)
1189.1(5)
2.45Ϫ28.24
Ϫ13 to 12
Ϫ13 to 13
Ϫ16 to 16
2
9.0940(8)
10.2778(9)
12.2877(10)
66.838(1)
83.946(1)
64.057(1)
946.42(14)
1.81Ϫ28.25
Ϫ12 to 12
Ϫ13 to 13
Ϫ16 to 16
2
˚
b (A)
˚
c (A)
α (°)
β (°)
γ (°)
90
90
114.265(1)
90
107.106(1)
90
90.767(2)
90
106.823(4)
90
3
˚
V (A )
1603.6(2)
2.48Ϫ28.27
Ϫ13 to 13
Ϫ12 to 12
Ϫ19 to 20
4
2560.6(4)
2.30Ϫ26.44
Ϫ20 to 18
Ϫ11 to 11
Ϫ23 to 24
4
2127.4(2)
2.04Ϫ28.23
Ϫ14 to 14
Ϫ17 to 18
Ϫ18 to 18
4
2207.7(4)
2.32Ϫ28.27
Ϫ14 to 14
Ϫ12 to 12
Ϫ26 to 26
4
2892.8(15)
1.69Ϫ28.11
Ϫ13 to 13
Ϫ23 to 23
Ϫ22 to 22
4
Θ (°)
h
k
l
Z
µ(Mo-Kα) (mmϪ1
)
0.288
4.865
5.318
5.886
6.517
5.718
4.493
Crystal size (mm)
0.20 ϫ 0.10 ϫ 0.05 0.25 ϫ 0.20 ϫ 0.15 0.20 ϫ 0.20 ϫ 0.15 0.20 ϫ 0.20 ϫ 0.15 0.15 ϫ 0.15 ϫ 0.10 0.15 ϫ 0.10 ϫ 0.05 0.15 ϫ 0.15 ϫ 0.10
Dcalcd. (g·cmϪ3
T (K)
)
1.227
1.786
173(2)
20004
5212
1.895
173(2)
26949
5489
2.006
173(2)
35350
5991
1.848
173(2)
21707
4397
1.894
173(2)
48267
5262
1.734
173(2)
60709
6827
173(2)
Reflections collected 15200
Independent
reflections
3600
Parameter
183
308
289
282
229
299
346
R1 [I Ͼ 2σ(I)]
R1 (overall)
wR2 [I Ͼ 2σ(I)
wR2 (overall)
Diff. peak/hole
0.0617
0.0646
0.1449
0.1496
0.482/Ϫ0.342
0.0394
0.0482
0.1037
0.1084
1.994/Ϫ1.678
0.0352
0.0357
0.0898
0.0900
1.564/Ϫ1.850
0.0474
0.0490
0.1022
0.1037
2.163/Ϫ1.798
0.0244
0.0260
0.0581
0.0585
3.488/Ϫ1.133
0.0418
0.0538
0.0968
0.1010
1.781/Ϫ1.276
0.0492
0.0542
0.1164
0.1180
2.097/Ϫ3.014
Ϫ3
˚
(e·A
)
CCDC
242558
242219
242220
242221
242222
242223
242224
[4]
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charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 1EZ, UK; Fax: (internat.) ϩ44-1223-336-033; E-mail:
deposit@ccdc.cam.ac.uk].
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4870
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 4859Ϫ4870