Reactivity of rhenium complexes containing a triamidoamine ligand toward samarium diiodide

Article abstract of DOI:10.1002/zaac.200500088

The reaction of [(HN₃N)ReOCl] (1) that contains the unsymmetric tren-based ligand HN₃N = ({C₆F₅NCH ₂CH₂}₂ NCH₂CH₂CH ₂NHC₆F₅)^2- with samarium diiodide leads to the formation of the iodide compounds [(N₃N)ReI] (2) and [(HN₃N)ReOI] (3). The reduction reaction also generates the unusual rhenium(IV) compound [(HN₃N*)ReX] (4, X = 0.35 % F and 0.65 % I,), where the amine ligand HN₃N* = ({C₆F ₅NCH₂CH₂}₂ NCH₂CH ₂CH₂NHC₆F₄)^3- is involved in an intramolecular C-F bond activation. The larger 6-membered metallacycle formed by the propylene amido substituent facilitates ortho metallation. All compounds have been characterized by single crystal X-ray analyses.

Full text of DOI:10.1002/zaac.200500088

Reactivity of Rhenium Complexes Containing a Triamidoamine Ligand Toward
Samarium Diiodide
Nadia C. Mösch-Zanetti* and Jörg Magull
Göttingen, Institut für Anorganische Chemie, Georg-August-Universität
Received February 18th, 2005.
Dedicated to Professor Herbert W. Roesky on the Occasion of his 70th Birthday
Abstract. The reaction of [(HN3N)ReOCl] (1) that contains the un-
symmetric tren-based ligand HN3N ({C6F5NCH2CH2}2
NCH2CH2CH2NHC6F4)3Ϫ is involved in an intramolecular C-F
bond activation. The larger 6-membered metallacycle formed by
the propylene amido substituent facilitates ortho metallation. All
compounds have been characterized by single crystal X-ray analy-
ses.
ϭ
NCH2CH2CH2NHC6F5)2Ϫ with samarium diiodide leads to the
formation of the iodide compounds [(N3N)ReI] (2) and
[(HN3N)ReOI] (3). The reduction reaction also generates the un-
usual rhenium(IV) compound [(HN3N*)ReX] (4, X ϭ 0.35 % F and
0.65 % I,), where the amine ligand HN3N* ϭ ({C6F5NCH2CH2}2
Keywords: Metallacycles; N ligands; Rhenium; Samarium
Introduction
plexes with an uncoordinated propylene substituent
(Scheme 1) [31], which is in contrast to the symmetrical
tren-based system [32, 33]. However, depending on the me-
tal ligand bond that needs to be cleaved, the N3N ligand
was also found to coordinate tetradentate. For example,
[(N3N)ReCl] is formed with the ligand in its trianionic
form, whereas in [(HN3N)ReBr2] the ligand is dianionic and
two bromine atoms remain at the metal center. These rhe-
nium complexes are formed by the unusual reaction of the
rhenium oxide [(HN3N)ReOX] with tantalum alkylidene
complexes of the type [TaCHCMe2PhX3(THF)2] (X ϭ Cl,
Br) [34], whereby oxygen transfer to tantalum and re-
duction to rhenium(IV) occurs. The intended transfer of an
alkylidene group from tantalum to rhenium was not ob-
served rendering the tantalum compound as unusual reduc-
ing agent. More common reducing agents such as sodium
amalgam, magnesium or zinc did not yield in any products.
In the search for a suitable reducing agent, we investigated
the reactivity of samarium diiodide toward [(HN3N)ReOX].
The divalent lanthanide reagent has attracted much interest
in organic transformations as a mild one-electron reducing
Not only since Schrock’s seminal discovery in 2003 that di-
nitrogen can be catalytically reduced under mild conditions
[1Ϫ3], complexes containing ligands with a tris(2-amino-
ethyl)amine (tren) backbone have held prominence in coordi-
nation and organometallic chemistry. In particular, deriva-
tives with sterically demanding substituents at the amido
nitrogen atom led to a wide variety of main group, tran-
sition and lanthanide metals complexes [4Ϫ20], that allow
for example activation of dinitrogen [1, 3, 21, 22], alkylidyne
formation by α,α-dehydrogenation of alkyl compounds or
by C,C-bond cleavage of cyclic alkyls [23, 24], and prep-
aration of terminal phosphido and arsenido compounds
[25Ϫ27]. Both, the C3 symmetry and the stability of the
chelate-5-rings imposed by such ligands are fundamental
requirements for the found reactivity. Triamidoamine li-
gands with variable substituents attached to the central ni-
trogen atom breaking the symmetry should therefore lead
to other reactivities. The coordination chemistry of tren
homologues such as bis(2-aminoethyl)(3-aminopropyl)am-
ine (baep) or (2-aminoethyl)bis(3-aminopropyl)amine
(abap) with late transition metals has been thoroughly in-
vestigated, where the insertion of additional CH2 groups
has profound structural and chemical consequences
[28Ϫ30].
We investigated the baep-based ligand with the sterically
demanding substituent C6F5 at the amido nitrogen atom
(C6F5NHCH2CH2)2NCH2CH2CH2NHC6F5 (H3N3N) em-
ploying an additional CH2 group in the backbone and
found considerably less stable chelate rings leading to com-
* Dr. N. C. Mösch-Zanetti
Inst. f. Anorg. Chemie der Universität
Tammannstraße 4
D-37077 Göttingen
E-mail: nmoesch@gwdg.de
Scheme 1
Z. Anorg. Allg. Chem. 2005, 631, 2585Ϫ2590
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N. C. Mösch-Zanetti, J. Magull
Scheme 2 Synthesis of [(N3N)ReI] (2)
agent [35Ϫ37]. In addition to the reducing capability, we
figured that the oxophilicity of the lanthanide metal should
facilitate oxygen transfer from rhenium to samarium.
Here, we describe the reaction of samarium diiodide with
[(HN3N)ReOCl] [31] producing several rhenium complexes
in the oxidation states III to V. Moreover, in one of them
the ligand is involved in an intramolecular C-F bond acti-
vation producing a complex with a rhenium fluorine bond.
Figure 1 Molecular view of [(N3N)ReI] (2). Hydrogen atoms have
been omitted for clarity.
the oxygen acceptor. The redox reaction was apparent by
the initial disappearance of the typical blue color of SmII
solutions. Samarium diiodide has been widely used in or-
ganic synthesis employing ketones and other oxygen con-
taining reagents in reductive cross-coupling reactions
[35Ϫ37].
Results and Discussion
Treatment of a THF solution of green [(HN3N)ReOX] (1)
with excess samarium diiodide (0.1 M in THF) at room
temperature for 12 hours gave a brown solution. After evap-
oration of the solvent and extraction of the resulting brown
powder, red crystals of [(N3N)ReI] (2) could be isolated in
17 % yield (Scheme 2). The compound is paramagnetic
analogous to previously described [(N3N)ReCl], which was
The molecular structure of 2 is shown in Figure 1, while
selected bond lengths and angles are given in Table 1 and
crystallographic data in Table 2. The structure is similar to
[{(C6F5NCH2CH2)3N}ReX] (X ϭ 40 % Cl, 60 % Br) that
contains the symmetrical tren ligand [33]. The influence of
the additional CH2 group in 2 on the geometry at the metal
center is negligible as shown by the bond lengths and angles
listed in Table 1, even though the six-membered metallacy-
cle formed by the coordinated propylene amido group has
an expected larger NaxϪReϪNeq angle (N2ϪRe1ϪN4
89.9(4)° compared to N1ϪRe1ϪN4 84.3(4)° and
N3ϪRe1ϪN4 80.9(3)°). The Re1-I2 bond length is with
prepared
employing
the
tantalum
compound
[TaCHCMe2PhCl3(THF)2] [31]. Due to the paramagnetism
and the unsymmetric ligand, characterization of compound
2 by NMR spectroscopy proved to be difficult. However,
mass spectrometry showing a peak at m/zϭ 969 with the
correct isotopic pattern for [M]ϩ and CHN analysis con-
firm the formation of the iodide. In addition, storage of a
toluene solution of 2 at Ϫ25 °C produced single crystals
suitable for X-ray diffraction analysis allowing the determi-
nation of its molecular structure.
˚
2.723(1) A in a similar range as in the few other crystallo-
graphically analyzed rhenium(IV) complexes that contain a
ReϪI bond [38, 39].
In the formation of complex 2, SmI2 plays presumably a
twin role by reducing the rhenium center and by acting as
We further investigated the reaction shown in Scheme 2
by varying the amount of added samarium diiodide as well
as the reaction time. Thus, treatment of a THF solution of
Scheme 3
Figure 2 Molecular view of compound [(HN3N)ReOI] (3).
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Reactivity of Rhenium Complexes Containing a Triamidoamine Ligand Toward Samarium Diiodide
1
[(HN3N)ReOCl] with one equivalent SmI2 at room tem-
perature for one hour gave also a brown solution. However,
after work up a mixture of a brown paramagnetic and a
green diamagnetic compound was obtained. The former
proved to be complex 2, whereas the green species analyzed
to the Finkelstein reaction [41]. After one week, H NMR
spectroscopy revealed still only 85 % conversion to 3.
Therefore, in the reaction involving samarium(II) a redox
process is presumably involved catalyzing the substitution
reaction. Separation of complexes 2 and 3 by crystallization
was not possible as they always co-crystallized in various
solvent mixtures. However, by exposing samples containing
mixtures of 2 and 3 to the laboratory atmosphere, pure 3
could be isolated after work up (Scheme 3).
1
as [(HN3N)ReOI] (3) as shown in Scheme 3. H and 19F
NMR spectroscopy data are consistent with the formu-
lation of 3 and are similar to those of 1. Moreover, the
green needles proved to be suitable for single crystal X-ray
diffraction analysis confirming the proposed structure.
The smaller amount of SmI2 leads only to partial re-
duction. The oxo iodide compound 3 represents the substi-
tution product, where the chlorine is replaced by an iodine
atom delivered by the samarium reagent. The electron im-
pact mass spectrum shows the molecular ions of 2 and 3,
respectively, but gives no indication of unreacted 1. This is
intriguing as substitution reaction at the ReVϭO center are
kinetically hindered [40]. This has been verified by refluxing
1 with excess NaI in acetonitrile, the inorganic analogue
The molecular structure of 3 determined by X-ray struc-
ture analysis shows the metal atom in a trigonal bipyrami-
dal environment with the iodide and the central nitrogen
N4 in the apical position thereby forcing the oxygen atom
in the equatorial position preventing coordination of the
third substituent (Figure 2). Analogous structural situations
are found in the structures of
1 as well as of
[{(C6F5NCH2CH2)2NMe}ReOCl] [31, 42]. The ReϪI bond
distance compares well with previously reported lengths of
this type [43, 44].
˚
Table 1 Selected Bond Lengths/A and Angles/° of Compounds [(N3N)ReI] (2), [{(C6F5NCH2CH2)3N}ReX](X ϭ Cl 0.6, Br 0.4)[33] and
[(HN3N)ReOI] (3).
[(N3N)ReI] (2)
[{(C6F5NCH2CH2)3N}ReX] [33]
[(HN3N)ReOI] (3)
Re1ϪI2
Re1ϪN1
Re1ϪN2
Re1ϪN3
2.723(1)
1.913(8)
1.945(8)
1.930(7)
2.147(9)
118.7(3)
117.5(3)
121.6(3)
84.3(4)
ReϪI
ReϪN1
ReϪN2
ReϪN4
2.684(1)
1.958(3)
1.954(3)
2.161(3)
1.694(3)
118.58(14)
79.23(12)
80.13(12)
98.60(12)
99.80(9)
161.60(8)
1.940(8)
1.913(8)
1.917(8)
2.173(8)
117.1(3)
116.0(3)
120.2(4)
Re1ϪN4
ReϪO1
N1ϪRe1ϪN2
N1ϪRe1ϪN3
N3ϪRe1ϪN2
N1ϪRe1ϪN4
N2ϪRe1ϪN4
N3ϪRe1ϪN4
N4ϪRe1ϪI2
N1ϪReϪN2
N2ϪReϪN4
N1ϪReϪN4
O1ϪReϪN4
O1ϪReϪI
N4ϪReϪI
89.9(4)
80.9(3)
175.7(3)
Table 2 Crystallographic Data and Structure Refinement of 2, 3 and 4
2
3·0.5 C7H8
1031.58
4
M
1244.90
1003.60
Formula
T/K
C46H38F15IN4Re
133(2)
monoclinic
P21/c
11.754(2)
17.786(4)
22.019(4)
C28.5H19F15IN4ORe
133(2)
C32H22F14.35I0.65N4Re
133(2)
monoclinic
P21/c
16.0605(6)
12.4985(6)
16.6479(6)
Crystal system
Space group
triclinic
¯
P1
˚
a/A
8.5068(7)
12.1953(11)
15.5134(13)
86.203(7)
85.963(7)
78.296(7)
1569.8(2)
2
˚
b/A
˚
c/A
α/°
β/°
γ/°
100.56(3)
106.512(3)
3
˚
U/A
4525.1(16)
4
1.827
3.468
3204.0(2)
4
2.081
4.532
Z
Dc/ mg mϪ3
2.182
4.976
µ/mmϪ1
F(000)
2θ/Range/°
Measured reflections
Unique reflections
Observed reflections
[I > 2σ(I)]
2420
1.88 to 22.51
28421
5899 (Rint ϭ 0.0925)
4004
978
2.10 to 24.63
34349
5256 (Rint ϭ 0.0761)
5003
1922
2.07 to 24.68
97528
5421 (Rint ϭ0.0765)
5347
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices [I > 2σ(I)]
R indices (all data)
5899 / 0 / 439
0.911
R1 ϭ 0.0447, wR2 ϭ 0.0877
R1 ϭ 0.0776, wR2 ϭ 0.0954
1.319 and Ϫ0.712
5256 / 0 / 441
1.092
R1 ϭ 0.0228, wR2 ϭ 0.0657
R1 ϭ 0.0241, wR2 ϭ 0.0662
1.515 and Ϫ1.234
5421 / 0 / 477
1.135
R1 ϭ 0.0313, wR2 ϭ 0.0803
R1 ϭ 0.0317, wR2 ϭ 0.0805
1.356 and Ϫ0.987
Ϫ3
˚
Largest diff. peak, hole / e A
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N. C. Mösch-Zanetti, J. Magull
In one of several attempts to separate 2 and 3 by crystal-
lisation, few additional red crystals appeared in cold tolu-
ene solutions which were shown to be the remarkable rhe-
nium(IV) compound [(HN3N*)ReX] (4) (X ϭ 0.35 F,
0.65 I; HN3N* ϭ ({C6F5NCH2CH2}2NCH2CH2CH2NHC6
F4)3Ϫ) as shown in Figure 3. Since we were unable to crys-
tallize further samples of this compound we can offer no
corroborative evidence for its formulation, but a brief dis-
cussion is included here because of its unusual nature. In
the C6F5 group attached to the propylene substituent CϪF
bond activation occurred in ortho position forming a 4-
membered metallacycle with a metal carbon and a metal
nitrogen bond. The hydrogen atom at nitrogen remains
bound. Thus, the ligand can be considered trianionic and
pentacoordinate. Furthermore, a fluoride ligand, which is
partially substituted by iodide is coordinated to the metal
atom. Therefore, the formal oxidation state of the metal can
be considered ReIV.
structure of a rhenium(IV) compound with a ReϪF bond de-
posited with the Cambridge Crystallographic Data Centre
˚
[45]. The ReϪC bond lengths is with 2.154(6) A in the same
range as in previously reported rhenium compounds con-
taining a ReϪC6F5 unit [46, 47].
The mechanism of the CϪF bond activation is not clear,
but formal oxidative addition of the CϪF bond to a re-
duced rhenium center is likely [48]. Further reactivity in-
volves substitution of the fluoride by iodide, probably due
to the abundance of iodide in the reaction solutions. Substi-
tution is probably fast once the rhenium atom is reduced to
ReIV. Abstraction of the ortho fluorine atom in a related
C6F5 substituted amido ligand, (C6F5NCH2CH2)2NMe,
has previously been observed [42]. By the reaction of
[Mo(NMe2)4] with (C6F5NHCH2CH2)2NMe, the molyb-
denum fluoro complex [{(C6F4(NMe2)NCH2CH2)2NMe}
MoF2] is formed, where the ortho fluorine atom is replaced
by a NMe2 group and the fluorine atom is bound to the
metal atom. Thus, the metallacycle formed is 5-membered
unlike in 4. The longer propylene substituent in 4 allows
the ortho carbon atom to bind to rhenium atom, whereas
in the ethylene substituents, the situation would be too
strained. In the molybdenum complex, this leads to replace-
ment of the ortho fluorine atom by NMe2. In both cases,
the existence of a CϪF bond in ortho position leads to non-
innocent behavior of the ligand, a fact that might be re-
sponsible for the obtained low yields of the reactions de-
scribed in this report and should be taken into consider-
ation for future design of such ligands.
The proton attached to N3 was located in difference
Fourier maps and refined. Furthermore, the angles about
N3 show a pyramidal geometry (see inset in Figure 3) rather
than a planar one as for N1 and N2 and the N3-Re bond
˚
length (2.279(5) A) is significantly longer than the amido
˚
rhenium bond lengths (1.93 Ϫ 1.98 A). The coordination at
the rhenium atom is distorted octahedral with the halide
ligand in apical position. The crystal chosen for X-ray crys-
tallography was composed of 35 % [(HN3N*)ReF] and
65 % [(HN3N*)ReI], since refinement of the axial position
as 0.35 F and 0.65 I gave a structure of high quality. The
thus determined bond lengths of ReϪF and ReϪI are
˚
2.108(13) and 2.688(1)A, respectively. The ReϪF bond is
Conclusion
slightly longer than that of [PNP]2[ReFBr5] (PNP ϭ Ph3Pϭ
ϩ
˚
NϭPPh3) , ReϪF 1.976(3) A), the only other X-ray crystal
This report demonstrates that excess samarium diiodide re-
duces [(HN3N)ReOCl] to [(HN3N)ReI]. Lower ratios of
samarium to rhenium leads to partial reduction and ad-
ditionally to substitution of the chloride by an iodide ligand
forming [(HN3N)ReOI]. The yields are lowered by side re-
actions involving CϪF bond activation in ortho position of
the C6F5 group attached to the propylene substituent.
Experimental Section
All manipulations were carried out under dry nitrogen using stand-
ard Schlenk line or glove box techniques. All solvents were purified
by standard methods and distilled under a nitrogen atmosphere
immediately prior to use. [(HN3N)ReOCl] was prepared according
to the literature procedure [31]. All other chemicals mentioned were
used as purchased from commercial sources.
Samples for mass spectrometry were measured on a BIO-RAD Di-
gilab FTS-7 mass spectrometer with a Finnigan MAT 95 and all
NMR spectra on a Bruker Avance 500 or 200. Elemental analyses
were performed by the Analytisches-Chemisches Laboratorium des
Instituts für Anorganische Chemie, Göttingen.
Figure 3 Molecular structure of [(HN3N*)ReX] (4) (X ϭ 0.35 F,
0.65 I) showing both the fluoride and iodide ligand. The inset
shows the pyramidal N3 atom within the metallacylce. Hydrogen
atoms have been omitted for clarity except the H atom at N3. Selec-
˚
ted bond lengths/A and angles/° of 4:
[(N3N)ReI] (2). To a solution of 0.44 g (0.5 mmol) of [(HN3N)Re-
OCl] in 15 mL of THF was added by syringe a solution of SmI2
(0.1 M in THF, 13,3 mL, 1.3 mmol) at room temperature. The solu-
tion was stirred for 12 h, whereby the color turned gradually from
ReϪI 2.688(1), ReϪF 2.108(13), ReϪN1 1.981(5), ReϪN2
1.925(5), ReϪN3 2.279(5), ReϪN4 2.177(4), ReϪC21 2.154(6),
N3ϪRe-C21 62.5(2), N4ϪReϪI 170.88(13).
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Reactivity of Rhenium Complexes Containing a Triamidoamine Ligand Toward Samarium Diiodide
green to brown-red. The solvent was evaporated, 50 mL of toluene
were added and the solution was filtered through a pad of Celite.
The thus obtained brown solution was evaporated to approximately
10 mL and stored at Ϫ25 °C. The product crystallized as red
needles suitable for X-ray crystal analysis (81 mg, 17 %). Ϫ MS(EI):
m/z (%) 969 (100, [M]ϩ). Ϫ Anal. calcd for C25H14F15IN4Re
(968.49): Calcd. C 31.00, H 1.46, N 5.78. Found: C 31.81, H 1.55,
N, 5.71.
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[(HN3N)ReOI] (3). To
a solution of 0.57 g (0.64 mmol) of
[(HN3N)ReOCl] in 15 mL of THF was added by syringe a solution
of SmI2 (0.1 M in THF, 6.4 mL, 0.64 mmol) at room temperature.
The solution was stirred for 1 hour, whereby the color turned
gradually from green to brown. The solvent was evaporated, 50 mL
of toluene were added and the solution was filtered through a pad
of Celite. The thus obtained brown solution was exposed to the
laboratory atmosphere for 10 minutes, filtered, evaporated to ap-
proximately 10 mL and stored at Ϫ25 °C. The product crystallized
as green needles, that were suitable for X-ray crystal analysis (Yield:
62 mg, 10 %). C25H15F15IN4ORe (985.5): Calcd. C 30.47, H 1.53,
N 5.69. Found: C 30.65, H 1.53, N 5.53 %.
1H NMR (CD3CN): δ 4.5 (br s, 1 H, NH), 4.21 (m, 2 H), 3.59 (m, 2 H), 3.34
(m, 6 H), 3.12 (m, 2 H), 2.14 (m, 2 H, NHCH2CH2CH2N). Ϫ 19F NMR
(CD3CN): δ 14.9 (m, 4 H, ReNC6Fortho), 3.75 (m, 2 F, HNC6Fmeta), 1.61 (t,
3
2 F, JFF ϭ 21 Hz, HNC6Fortho), Ϫ2.3 Ϫ Ϫ2.8 (m, 6 F, ReNC6Fpara and
3
4
ReNC6Fmeta), Ϫ10.56 (tt, 1 F, JFF ϭ 22 Hz, JFF ϭ 7 Hz, HNC6Fpara). Ϫ
MS(EI): m/z (%) 986 (100, Mϩ).
X-ray crystallographic determinations
Crystals of compounds 2, 3 and 4 were taken from the solution,
covered with oil and mounted on glass fibres at room temperature.
Data were collected on a Stoe IPDS II-array detector system in-
strument with graphite-monochromated Mo-Kα radiation (λ ϭ
˚
0.71073 A). The structures were solved by direct methods using
SHELXS-97[49] and refined against F2 on all data by full-matrix
least-squares with SHELXL-97 [50]. All non-hydrogen atoms were
refined anisotropically. For 4, the hydrogen atom H3N was located
in difference Fourier maps and refined. All other hydrogen atoms
were included in the model at geometrically calculated positions
and refined using a riding model.
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Data Centre as a supplementary publication no. CCCD 262729 (2),
262728 (3) and 262727 (4). Copies of the data can be obtained free
of charge on application to CCDC, 12 union Road, Cambridge
CB21EZ, UK (fax: ϩ(44)1223-336-033; email: deposit@ccdc.cam.-
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