Reactivity of B(C6F5)3 with oxovanadium(v) complexes VOL3 (L = OCH2CF3, NEt2): Formation of the organometallic vanadium(v) complex [VO(μ-OCH2CF3)(OCH2CF3) (C6F5)]2 and the Lewis acid adduct

Article abstract of DOI:10.1002/ejic.200390086

Treatment of the oxovanadium(v) complex [VO(OCH₂CF₃)₃]₂ (3) with the Lewis acid B(C₆F₅)₃ leads to aryl/alkoxy group exchange and formation of the unexpected organometallic oxovanadium(v) [VO(μ-OCH₂CF₃)(OCH₂CF₃) (C₆F₅)]₂ (1), while reaction of B(C₆F₅)₃ and [VO(NEt₂)₃] produces the Lewis acid adduct [(Et₂N)₃VO·B(C₆F₅) ₃] (2). The crystal structures of 1, 2 and 3 were determined, ⁵¹V NMR chemical shifts for complexes 1-3 and [VO(NEt₂)₃] are discussed. A concentration-dependant monomer-dimer equilibrium for 3 is observed in solution. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

Full text of DOI:10.1002/ejic.200390086

FULL PAPER
Reactivity of B(C6F5)3 with Oxovanadium( ) Complexes VOL3
V
(L ؍ OCH2CF3, NEt2): Formation of the Organometallic Vanadium( )
V
Complex [VO(µ-OCH2CF3)(OCH2CF3)(C6F5)]2 and the Lewis Acid Adduct
[(Et2N)3VO·B(C6F5)3]
Fabien Wolff,[a] Robert Choukroun,*[a] Christian Lorber,[a] and Bruno Donnadieu[a]
Keywords: N ligands / O ligands / Boranes / Structure determination / Vanadium
Treatment of the oxovanadium(
(3) with the Lewis acid B(C6F5)3 leads to aryl/alkoxy group
exchange and formation of the unexpected organometallic
V
) complex [VO(OCH2CF3)3]2
structures of 1, 2 and 3 were determined. 51V NMR chemical
shifts for complexes 1−3 and [VO(NEt2)3] are discussed. A
concentration-dependant monomer-dimer equilibrium for 3
is observed in solution.
oxovanadium(
V)
[VO(µ-OCH2CF3)(OCH2CF3)(C6F5)]2 (1),
while reaction of B(C6F5)3 and [VO(NEt2)3] produces the ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Lewis acid adduct [(Et2N)3VO·B(C6F5)3] (2). The crystal
Germany, 2003)
the chemical shift measurements of the mixed series
[VOL2(OiPr)] or [VOL(OiPr)2], the relative Lewis acidity of
[VO(OCH2CF3)3] toward [VO(NEt2)3] can be inferred.[7Ϫ9]
Introduction
The reactivity and bonding of tris(pentafluorophenyl)-
borane B(C6F5)3 to transition metal complexes continues to
be a field of intense interest in both fundamental and ap-
plied chemistry.[1] The Lewis acid properties of B(C6F5)3
influence the reactivity greatly, and CϪF···metal interac-
tions or perfluoroaryl/alkyl exchange reactions have been
observed.[2] More recently, the reactivity of tris(penta-
fluorophenyl)borane towards different oxo metal complexes
MϭO has been investigated and oxo-group adducts isol-
ated, particularly [(acac)2VO·B(C6F5)3].[3] Additionally, a
Lewis acid adduct derived from the coordination of an al-
kylaluminium complex to the terminal oxygen of the oxov-
anadium() complex [VO(CH2SiMe3)3Ϫx(OSiPh3)x (x ϭ
0Ϫ3)] was observed by multinuclear NMR spectroscopy
(17O, 51V).[4]
Results and Discussion
Synthesis and Molecular Structures of [VO(µ-OCH2CF3)-
(OCH2CF3)(C6F5)]2 (1) and [VO(OCH2CF3)3]2 (3)
The reaction of [VO(OCH2CF3)3]2 (3) in pentane with
B(C6F5)3 gives the dimeric organometallic complex [VO(µ-
OCH2CF3)(OCH2CF3)(C6F5)]2 (1), as shown in Equa-
tion (1). Complex 1 is the second example[10a] of an organo-
metallic oxovanadium() to be fully characterized by an
X-ray structure determination (Figure 1).
We are interested in vanadium chemistry[5] and, among
our recent work, we have identified a CϪF···V interaction
in vanada()azirine complexes isolated from a new type of
reaction between [VCp2] and the activated nitrile
RCϵN·B(C6F5)3.[6] We have recently extended our study to
the oxovanadium() complexes [VO(NEt2)3][7] and
[VO(OCH2CF3)3],[8] and have found that the reactivity of
these complexes is influenced by the substituents L (L ϭ
NEt2, OCH2CF3) attached to the vanadium center. In
(1)
The formation of this organometallic oxovanadium()
complex is due to an exchange reaction between the
B(C6F5)3 and the fluoroalkoxy ligand OCH2CF3. Such an
exchange is not unique and is already known in zirconium
chemistry.[2aϪ2c] The distance of the vanadium atom to the
˚
basal plane O(2), C(11), O(3), OЈ(2) in 1 is 0.5476(19) A.
The molecular structure establishes that 1 is a complex with
a five-coordinate distorted square pyramidal geometry with
the three oxygen atoms and the Cipso atom of the perfluoro-
phenyl group occupying the basal site (79.6% on the Berry
pseudorotation path between D3h and C4v [11]) for the vana-
1
agreement with the H NMR scale that we deduced from
[a]
Laboratoire de Chimie de Coordination du CNRS,
205 route de Narbonne, 31077 Toulouse Cedex, France
Fax: (internat.) ϩ 33-5/61553003
˚
dium center. The VϪC distance [2.066(4) A] is in the ex-
E-mail: choukrou@lcc-toulouse.fr
pected range for such a bond.[10] In order to compare the
628
 2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim 1434Ϫ1948/03/0204Ϫ0628 $ 20.00ϩ.50/0 Eur. J. Inorg. Chem. 2003, 628Ϫ632

Reactivity of B(C6F5)3 with Oxovanadium(V) Complexes VOL3
FULL PAPER
of the OϪVϪO angles containing O(3), O(4) and OЈ(2)
around the vanadium atom being 348.6° (18.7% on the
Berry pseudorotation path[11]).
Both complexes 1 and 3 are centrosymmetric dimers in
the solid state. A disymmetrical bridge VϪO(R)ϪV is ob-
served for 3, and the average VϪO bond length is similar
˚
˚
˚
to that in 1 (1: 1.997 A (av); 3: 1.843(2) A, 2.296(3) A]. The
other VϪOR (terminal) and VϭO distances around the va-
nadium atom in 1 and 3 are essentially the same (1: 1.748(3)
˚
˚
˚
˚
˚
A, 1.568(3) A; 3: 1.757(3) A and 1.771(3) A, 1.579(3) A, re-
spectively).
Although the VϪOϪC angle of the terminal OR group
for 1 (134.8°) is similar to other VϪOϪC angles observed
in different vanadium alkoxides ([VO(OtBu)3]: 139.0°
(av),[12] [V(OiPr)4]2: 126.27°, 134.67°, 140.27°,[13] [VO(O-
SiPh3)3]: VϪOϪSi (av) 155° [14]) the VϪOϪC angles of 3 are
more acute (130.5° (av)), suggesting a poorer pπ-dπ overlap
˚
Figure 1. Molecular structure of 1 with selected bond lengths (A)
and angles (°), showing the labeling scheme; hydrogen atoms are between the oxygen atoms and the vanadium center of 3. It
omitted for clarity: VϪC(11) 2.069(5), VϪO(1) 1.569(4), VϪO(2)
is worth noting that in a previous work published by one
1.998(3), VϪO(2)Ј 1.995(3), VϪO(3) 1.748(3); O(2)ϪVϪO(2)Ј
of us, a synthetic route for the preparation of the phenylva-
nadium() complexes [PhVO(OiPr)2] and [PhVOCl(OiPr)]
was reported using LiPh or HgPh2 as phenylating agents,
although these vanadium complexes are unstable and de-
compose with time.[15] Attempts to prepare the phenyl ana-
logue [PhVO(OCH2CF3)2] by these routes were unsuccess-
ful, in contrast to the easy formation of 1 using B(C6F5)3
as an alkylating agent.
72.03(15), O(1)ϪVϪO(3) 105.99(18), O(1)ϪVϪC(11) 100.7(2),
O(3)ϪVϪC(11) 90.50(18), O(2)ϪVϪC(11) 87.77(17), O(2)ЈϪ
VϪC(11) 141.13(18), V-[O(2)ϪVЈ 107.97(15), VϪO(2)ϪC(1)
126.4(3), VϪO(3)ϪC(3) 134.8(3)
Synthesis and Molecular Structure of [(Et2N)3VO·B(C6F5)3]
(2)
Treatment of the more basic complex [VO(NEt2)3] with
B(C6F5)3 gave the oxovanadium Lewis acid adduct com-
pound [(Et2N)3VO·B(C6F5)3] (2) as dark red crystals [Equa-
tion (2)].
(2)
The crystal structure of complex 2 (Figure 3) reveals the
coordination of the Lewis acid B(C6F5)3 to the VϭO moi-
ety. Both vanadium and boron atoms have a pseudo-tetra-
hedral structure (OϪVϪN and NϪVϪN average angles
113.3° and 105.4° respectively; OϪBϪC and CϪBϪC aver-
age angles 106.6° and 112.3°, respectively). The longer Vϭ
˚
Figure 2. Molecular structure of 3 with selected bond lengths (A)
and angles (°), showing the labeling scheme; hydrogen atoms are
omitted for clarity: VϪO(1) 1.579(2), VϪO(2) 2.297(2), VϪO(3)
1.757(2), VϪO(4) 1.771(2), VϪOЈ(2) 1.843(2); VϪO(2)ϪVЈ
108.85(9), O(2)ϪVϪO(2)Ј 71.15(9), O(1)ϪVϪO(2) 170.63(11),
O(1)ϪVϪO(2)Ј 99.49(11), O(1)ϪVϪO(3) 101.69(12), O(1)ϪVϪ
O(4) 102.97(12), VϪO(2)ϪC(1) 124.15(19), VЈϪO(2)ϪC(1)
126.3(2), VϪO(3)ϪC(3) 131.0(2), VϪO(4)ϪC(5) 129.9(3)
˚
O distance of 1.6983(16) A and the shorter BϪO bond
˚
length [1.498(3) A] indicate the reduction in bond order of
the VϭO moiety and the formation of a boronϪoxygen
single bond with a nearly linear VϪOϪB angle of 174.87
(15)°. It is worth noting that: i) the VϪO bond length indic-
ates the formation of a single VϪO bond {cf. VϪO (for
terminal OR group) and VϭO distances in [VO(OR)3]:
˚
˚
˚
˚
1.753 A (av), 1.790 A and 1.595(2) A and 1.591 A (av) for
vanadium-oxygen bond lengths with the parent compound, R ϭ tBu and Me, respectively};[11] ii) the BϪO bond length
a single-crystal X-ray diffraction study was performed on 3 is shorter than that observed in F3B·OPPh3 [1.516(3) A]
(Figure 2). The vanadium centre is trigonal bipyramidal, as (for comparison, in [(acac)2VO·B(C6F5)3],[3a] VϭO 1.648(1)
[16]
˚
˚
˚
seen by the larger O(1)ϪVϪO(2) angle of 170.6°, the sum A, BϪO 1.527(2) A, VϪOϪB 168.9(1)°].
Eur. J. Inorg. Chem. 2003, 628Ϫ632
629

F. Wolff, R. Choukroun, C. Lorber, B. Donnadieu
FULL PAPER
Ϫ625 ppm and Ϫ570 ppm, respectively) confirm the above
1H NMR results, i.e. a concentration-dependant monomer-
dimer equilibrium. The values observed at δ ϭ Ϫ481 ppm
for the dimer 1 and δ ϭ Ϫ570 ppm for dimer 3 show a
deshielding effect for 1 due to the replacement of a fluoroal-
koxy group with an alkyl perfluorophenyl group as a purely
σ-bonding ligand. From the relative overall electron-with-
drawing capability of both ligands already pointed out
above, the 51V chemical shifts of 1 and 3 follow an ‘‘inverse’’
halogen dependence, i.e. a shielding of the metal in the d0
configuration upon increasing the electronegativity of the
ligands attached to the coordination center.[18Ϫ21]
The 51V chemical shifts for [VO(NEt2)3] and the borane
adduct 2 (δ ϭ Ϫ205 ppm and ϩ57 ppm, respectively) are
puzzling. If we consider that the sp2 hybridization observed
for the planar nitrogen atom of the NEt2 ligands in 2 is
unchanged in [VO(NEt2)3] before borane coordination
(based on recent X-ray diffraction studies of different dial-
kylamido vanadium() and vanadium() complexes re-
cently carried out by our group[22] and others[23]) the ob-
served deshielding shift could be attributed mainly to
a decrease in electron density at the vanadium atom when
the Lewis acid B(C6F5)3 is attached to the oxygen atom. A
similar consequence of poorer π-donation from O to V is
˚
Figure 3. Molecular structure of 2 with selected bond lengths (A)
and angles (°), showing the labeling scheme; hydrogen atoms are
omitted for clarity: VϪO 1.6983(16), VϪN(11) 1.8255(19),
VϪN(12) 1.8285(19), VϪN(13) 1.8211(19), OϪB 1.498(3);
VϪOϪB 174.87(15), OϪV-(N11) 104.03(9), OϪVϪN(12)
106.39(9), OϪVϪN(13) 112.97(8), OϪBϪC(111) 107.41(19),
OϪBϪC(121) 105.49(18), OϪBϪC(131) 106.60(18).
also
observed
in
the
Lewis
acid
adducts
1H and 51V NMR Spectroscopy
[VO(CH2SiMe3)3Ϫx(OSiPh3)x (x ϭ 0Ϫ3)] with Al(CH2Si-
The H NMR spectrum of 1 at room temperature shows Me3)3.[4b]
a unique quadruplet resonance for the OCH2CF3 group
(δ ϭ 4.50 ppm), which reflects a rapid exchange of both
1
Conclusion
terminal and bridging OR groups in solution. This persists
at low temperature (in [D8]toluene at Ϫ90 °C), indicating
We have demonstrated that the reactivity of the Lewis
acid B(C6F5)3 with [VOL3] is modulated by the electronic
properties of the ligands L. The reaction with VϭO is facil-
itated by the nucleophilic oxo group when L is an electron-
donating dialkylamido group whereas formation of the or-
ganometallic complex 1 containing a VϪC6F5 bond is pro-
moted by an exchange reaction with B(C6F5)3 when L is
OCH2CF3 (an electron-withdrawing group). Potentially,
this provides a suitable synthetic route for the development
of new organometallic fluoroalkoxy complexes.
1
that the exchange is extremely rapid.[9] In contrast the H
NMR spectrum of 3 is concentration dependant, a well-
known aspect of the monomer-dimer/polymer behavior in
early transition metal alkoxides.[9,17] At low concentration,
3 is monomeric (δ ϭ 4.56 ppm) whereas it dimerizes at
higher concentration (δ ϭ 4.95 ppm) showing an equilib-
rium between both forms in solution (see Exp. Sect.). The
upfield shift of the methylene protons observed for 1 (δ ϭ
4.50 ppm) relative to 3 (δ ϭ 4.95 ppm) reflects the differ-
ence between an OR group which allows some π-donation
and a purely electron-withdrawing σ-group (C6F5). The rel-
ative overall electron-withdrawing capability of both ligands
(OCH2CF3 Ͼ C6F5) was deduced from these chemical
shifts. Addition of one equivalent of B(C6F5)3 to 1, and
Experimental Section
General Remarks: All manipulations were carried out using stand-
ard Schlenk line or drybox techniques under an atmosphere of ar-
gon. Starting materials were purchased from Aldrich Inc. or Fluka
Inc. and used without further purification. Solvents were refluxed
and dried over appropriate drying agents under an atmosphere of
argon, collected by distillation and stored in a drybox over activ-
1
monitoring of the reaction by H and 19F NMR spectro-
scopy for two days, confirmed that vanadium complex re-
mains unchanged.
The 51V NMR spectra for the series 1, 2, 3 and
[VO(NEt2)3] were recorded in C6D6 solution at two differ-
ent concentrations (see Exp. Sect.) to ensure that associ-
ation phenomena do not interfere with the observed chem-
ical shifts. We also verified that the synthesis of 2 gives only
one compound in solution. For complex 1, the preparative
solution shows the peak assigned to the formation of 1
(isolated in high yield) and three other minor 51V signals
that could not be assigned. The two different 51V NMR
˚
ated 4-A molecular sieves. Deuterated solvents were degassed and
˚
dried over activated 4-A molecular sieves. NMR spectroscopic data
were recorded using Bruker AMX-400, DPX-300 and AC-200 spec-
trometers, and referenced internally to residual protonated-solvent
(1H) resonances and are reported relative to tetramethylsilane (δ ϭ
0 ppm). 19F NMR (188.298 MHz) spectra were recorded on a
Bruker AC-200 spectrometer (reference CF3CO2H). The
AAЈMMЈX system in the 19F NMR spectrum of compound 2 was
signals observed for 3 at low and high concentration (δ ϭ simulated using the MestRe-C sofware package. 51V NMR
630 Eur. J. Inorg. Chem. 2003, 628Ϫ632

Reactivity of B(C6F5)3 with Oxovanadium(V) Complexes VOL3
FULL PAPER
(105.17 MHz) spectra were recorded on a Bruker AMX-400 spec-
trometer (reference VOCl3 in C6D6: 9:1). Infrared spectra were pre-
pared as KBr pellets under argon in a glove box and were recorded
on a PerkinϪElmer Spectrum GX FT-IR spectrometer. Infrared
data are quoted in wavenumbers (cmϪ1). Elemental analyses were
performed at the Laboratoire de Chimie de Coordination (Toul-
ouse, France).
(t, 3JF,H ϭ 8.0 Hz, OCH2CF3), Ϫ40.7 (d, 3J ϭ 85.6 Hz, o-F, C6F5),
Ϫ70.3 (t, J ϭ 11.3 Hz, p-F, C6F5), Ϫ84.2 (br. s, m-F, C6F5) ppm.
3
51V NMR (C6D6) (2 experiments as for 1H NMR): δ ϭ Ϫ481 ppm.
IR (KBr): ν˜ ϭ 2359 (m), 1636 (w), 1540 (s), 1510 (s), 1466 (m),
1359 (w), 1268 (s, br), 1182 (s, br), 1074 (s, br), 1035 (m, br), 962
(s), 839 (m), 746 (m), 669 (m), 581 (w), 497 (w). C20H8F22O6V2:
calcd. C 27.80, H 0.93; found C 27.80, H 0.85.The 1H, 11B and 51
V
NMR spectra of the filtrate, after workup, show peaks for three
minor unidentified species (1H NMR: δ ϭ 4.09, 3.86, 3.74 ppm.
11B NMR: δ ϭ 42, 27, 25 ppm. 51V: δ ϭ Ϫ531, Ϫ840, Ϫ885 ppm).
Some of these high-field resonances could correspond to
species where fluorines are attached directly to the vanadium
atom.[20]
[VO(NEt2)3] and 3 were prepared as described previously[7,8] and
B(C6F5)3 according to the literature.[24] Crystals of 3 were obtained
by sublimation under vacuo (10Ϫ2 Torr) at 40 °C. The 51V NMR
spectrum of [VO(NEt2)3] (EPR silent) was recorded in C6D6 at dif-
ferent ratios (9:1; 1:9) and found at δ ϭ Ϫ205 ppm (we note that
the value published by Rehder et al. for [VO(NEt2)3] at δ ϭ
Ϫ389 ppm,[20] as a neat liquid, differs notably from our result).
[VO(OCH2CF3)3]: 2 experiments: a) 100 mg and b) 2 mg in 0.6 mL
C6D6: a) 1H NMR (C6D6): δ ϭ 4.95 (q, 3JH-F ϭ 8.3 Hz, CH2) ppm.
[V(NEt2)3O·B(C6F5)3] (2):
A solution of B(C6F5)3 (362 mg,
0.70 mmol) in pentane (4 mL) was added dropwise to a solution
of [VO(NEt2)3] (200 mg, 0.70 mmol) in pentane (3 mL) at room
temperature. After 4 days at room temperature, dark red crystals
were filtered off, washed with pentane and dried under vacuum
(122 mg, 22%). In another experiment, a solution of B(C6F5)3
(15 mg, 0.03 mmol) in C6D6 (0.3 mL) was added to a solution of
3
19F NMR (C6D6): δ ϭ Ϫ0.8 (t, JF-H ϭ 8.3 Hz, CF3) ppm. 13C
NMR (C6D6): δ ϭ 124.0 (1JC,F ϭ 279.3 Hz, CF3), 80.6 (2JC,F
ϭ
36.1 Hz, CH2) ppm. 51V NMR (C6D6): δ ϭ Ϫ570. b) 1H NMR
(C6D6): δ ϭ 4.55 (q, 3JH-F ϭ 8.3 Hz, CH2) ppm. 19F NMR (C6D6):
3
δ ϭ Ϫ0.2 (t, JF-H ϭ 8.3 Hz, CF3) ppm. 51V NMR (C6D6): δ ϭ
1
[VO(NEt2)3] (8 mg, 0.03 mmol) in C6D6 (0.3 mL). The H and 51V
Ϫ625. VO(NEt2)3 ppm. 1H NMR (C6D6): δ ϭ 3.74 (q, 3J ϭ 6.9 Hz,
CH2), 1.25 (t, 3J ϭ 6.9 Hz, CH3) ppm. 13C NMR (C6D6): δ ϭ 52.7
(CH2), 16.5 (CH3) ppm. 51V NMR (C6D6): δ ϭ Ϫ205 ppm.
NMR of the solution were identical to those of isolated 2 in the
same solvent. 1H NMR (C6D6): δ ϭ 3.59 (q, 3J ϭ 7.0 Hz, 6 H,
CH2CH3), 0.62 (t, 3J ϭ 7.0 Hz, 9 H, CH2CH3) ppm. 13C NMR
[VO(C6F5)(µ-OCH2CF3)(OCH2CF3)]2 (1): A solution of B(C6F5)3 (C6D6): δ ϭ 151.2, 147.5, 140.1, 138.5, 136.1 [B(C6F5)3], 54.7
(281 mg, 0.55 mmol) in pentane (4 mL) was added dropwise to a
solution of [VO(OCH2CF3)3] (200 mg, 0.55 mmol) in pentane (AAЈMMЈX system, JAM
(3 mL) at room temperature. The reaction mixture was stirred for 9.0 Hz, 2F, o-F, B(C6F5)3], Ϫ82.9 (AAЈMMЈX system, JMЈX
(CH2CH3), 14.6 (CH2CH3) ppm. 19F NMR (C6D6): δ ϭ Ϫ56.7
3
5
ϭ
3JAЈMЈ ϭ Ϫ24.5, JAЈM
ϭ
5JAMЈ
ϭ
3
ϭ
2 h at room temperature and then cooled in the freezer overnight.
Red crystals were filtered off, washed with pentane and dried under
3JMX ϭ Ϫ20.8 Hz, p-F, B(C6F5)3], Ϫ88.7 (AAЈMMЈX system,
3JAM ϭ 3JAЈMЈ ϭ Ϫ24.5, 5JAЈM ϭ JAMЈ ϭ 9.0, 4JMMЈ ϭ Ϯ 3.1 Hz,
5
vacuum (152 mg, 64%). 1H NMR (2 experiments at 5 mg and
2 F, m-F, B(C6F5)3] ppm. 11B NMR (C6D6): δ ϭ 1.2. 51V NMR
(C6D6): δ ϭ 57 ppm. IR (KBr): ν˜ ϭ 2983 (m), 2944 (m), 2360 (m),
3
60 mg in 0.6 mL C6D6 give same δ values): δ ϭ 4.50 (q, JH,F
ϭ
8.0 Hz, CH2CF3). 13C NMR (C6D6): δ ϭ 149.2, 146.3, 145.2, 142.2, 2341 (m), 1643 (m), 1515 (s), 1458 (s, br), 1374 (m), 1358 (m), 1279
138.8, 134.8 (C6F5) 123.5 (q, JC,F ϭ 279.2 Hz, OCH2CF3), 79.4 (m), 1182 (w), 1144 (m), 1096 (s, br), 972 (s, br), 909 (w), 848 (w),
1
2
(q, JC,F ϭ 36.2 Hz, OCH2CF3) ppm. 19F NMR (C6D6): δ ϭ Ϫ0.2 793 (m), 771 (m), 738 (w), 676 (m), 626 (m), 613 (w), 574 (w), 478
Table 1. Crystallographic data, data collection and refinement parameters for compounds 1, 2 and 3
Compound
1
2
3
Chemical formula
Molecular weight
T (K)
C10H4F11O3V
432.07
180
monoclinic
P21/c
12.462(5)
12.311(5)
9.250(5)
95.175(5)
1413.3(11)
0.844
4, 2.031
8096
1986
C30H30BF15N3OV
795.32
180
monoclinic
P21/c
10.226(1)
19.575(2)
17.178(2)
104.85(1)
3323.6(5)
0.413
4, 1.589
26141
6213
C6H6F9O4V
364.05
180
monoclinic
P21/n
8.4858(8)
10.0566(7)
14.498(2)
92.59(1)
1235.9(2)
0.928
4, 1.956
6940
1752
Crystal system
Space group
˚
a (A)
˚
b (A)
˚
c (A)
β (deg)
˚
V (A)
µ (mmϪ1
)
Z, Dcalcd. (g/cm3),
Measured reflections
Unique reflections
Rint
0.0520
0.0575
0.0489
no. of variables
tmin. Ϫ tmax.
254
466
208
0.2970Ϫ0.7380
1.069
0.6080Ϫ0.8830
0.930
0.3930Ϫ0.7920
1.038
GOF on F2
R1 [I Ͼ 2σ(I)]
wR2 [I Ͼ 2σ(I)]
R1 (all data)
wR2 (all data)
ρmin. and ρmax., e·A
0.0476
0.1299
0.0580
0.1370
0.0386
0.0777
0.0711
0.0875
0.0384
0.1085
0.0428
0.1126
Ϫ3
˚
0.942 and Ϫ0.478
0.255 and Ϫ0.290
0.399 and Ϫ0.354
Eur. J. Inorg. Chem. 2003, 628Ϫ632
631

F. Wolff, R. Choukroun, C. Lorber, B. Donnadieu
FULL PAPER
Soc., Dalton Trans. 1999, 3185. [2f] V. V. Burlakov, P. Arndt, W.
Baumann, A. Spannenberg, U. Rosenthal, A. V. Letov, K. A.
Lyssenko, A. A. Korlyukov, L. I. Strunkina, M. Kh. Minach-
eva, V. B. Shur, Organometallics 2001, 20, 4072. [2g] G. M. Bene-
(w). C30H30BF15N3OV: calcd. C 45.28, H 3.77, N 5.28; found C
45.33, H 3.66, N 5.07).
X-ray Analysis of 1, 2 and 3: Data were collected at low temperature
(T ϭ 180 K) for the three compounds, on a IPDS STOE diffracto-
meter equipped with an Oxford Cryosystems Cryostream Cooler
Device and using graphite-monochromated Mo-Kα radiation (λ ϭ
dikt, B. L. Goodall, S. Iyer, L. H. McIntosh III, R. Mimna, L.
[2h]
F. Rhodes, Organometallics 2001, 20, 2565.
N. Kleigrewe,
T. Brackemeyer, G. Kehr, R. Frol¨ıch, G. Erker, Organometallics
[2i]
2001, 20, 1952.
Y. Sunn, R. E. H. Spence, W. E. Piers, M.
˚
0.71073 A). Final unit-cell parameters were obtained by means of
Parvez, G. P. A. Yap, J. Am. Chem. Soc. 1997, 119, 5132.
a least-squares refinement of a set of well-defined reflections; crys-
tal decay was monitored during data collection and no significant
fluctuations of intensities were observed. The structures were
solved by direct methods using SIR92,[25] refined by least-squares
procedures on F2 with the aid of SHELXL-97[26] included in the
program package WinGX version 1.63.[27] The atomic scattering
factors were taken from the International Tables for X-ray Crystal-
lography.[28] All hydrogens atoms were located on difference Fourier
maps and refined using a riding model with an isotropic thermal
parameter fixed at 20% higher than those of the carbons atoms to
which they are connected. For 3 a disorder was located on the
fluorine group: the fluorine atoms were found to be statistically
disordered over two distinct orientations with an occupancy ratio
of 55/45. Some restraints on interatomic CϪF distances and
FϪCϪF angles were imposed in order to reach a reasonable geo-
metry and regularize the motion of the F atoms. For the three
compounds all non-hydrogens atoms were refined anisotropically
and, in the last cycles of refinement, a weighting scheme was used
whose weights were calculated from the following formula: w ϭ
1/[σ2(F2o) ϩ (aP)2 ϩ bP] where P ϭ (F2o ϩ 2F2c)/3. For all structures
the criteria for a satisfactory complete analysis were a ratio of rms
shift to standard deviations of less than 0.1 and no significant resid-
ual electronic densities in the final differences maps. Drawings of
molecules were performed with the program ORTEP32[29] with
50% probability displacement ellipsoids for non-hydrogen atoms.
The crystallographic data of 1, 2 and 3 are summarized in Table 1.
CCDC-190469 (1) -190470 (2) and -190471 (3) contain the supple-
mentary crystallographic data for this paper. These data can be
obtained free of charge at www.ccdc.cam.ac.uk/conts/
retrieving.html [or from the Cambridge Crystallographic Data
Center, 12, Union Road, Cambridge CB2 1EZ, UK; fax: (internat.)
ϩ44Ϫ1223/336Ϫ033; E-mail: deposit@ccdc.cam.ac.uk].
[3] [3a]
J. R. Galsworthy, M. L. H. Green, M. Müller, K. J. Prout,
[3b]
J. Chem. Soc., Dalton Trans. 1997, 1309.
J. R. Galsworthy,
J. C. Green, M. L. H. Green, M. J. Müller, J. Chem. Soc., Dal-
ton Trans. 1998, 15. [3c] L. H. Doerrer, J. R. Galsworthy, M. L.
H. Green, M. A. Leech, J. Chem. Soc., Dalton Trans. 1998,
2483.
[4a] F. J. Feher, R. L. Blanski, Organometallics 1993, 12, 958. [4b]
F. J. Feher, R. L. Blanski, J. Am. Chem. Soc. 1992, 114, 5886.
R. Choukroun, C. Lorber, B. Donnadieu, Organometallics
2002, 21, 1124 and references therein.
[4]
[5]
[6]
R. Choukroun, C. Lorber, B. Donnadieu, Chem. Eur. J. 2002,
8, 2700.
R. Choukroun, D. Gervais, Inorg. Chim. Acta 1978, 27, 163.
R. Choukroun, A. Dia, D. Gervais, Inorg. Chim. Acta 1979,
34, 211.
[7]
[8]
[9]
C. Campbell, S. G. Bott, R. Larsen, W. G. Van der Sluys, Inorg.
Chem. 1994, 33, 4950.
[10] [10a]
M. Vivanco, J. Ruiz, C. Floriani, A. Chiesi-Villa, C. Riz-
[10b]
zoli, Organometallics 1993, 12, 1802.
Turner, Organometallics 1997, 16, 2495.
Arnold, Organometallics 1996, 15, 5260.
V. J. Murphy, H.
[10c]
C. P. Gerlach, J.
P. T. Witte, A.
[10d]
Meetsma, B. Hessen, J. Am. Chem. Soc. 1997, 119, 10561.
R. R. Holmes, Prog. Inorg. Chem. 1984, 32, 119.
J. Spandt, I. Brüdgam, H. Hartl, Z. Anorg. Allg. Chem. 2000,
626, 2125.
R. Kempe, A. Spannenberg, New Crystal Structures 1997,
212, 485.
F. J. Feher, J. F. Walzer, Inorg. Chem. 1991, 30, 1689.
R. Choukroun, S. Sabo, J. Organomet. Chem. 1979, 182, 221.
M. A. Beckett, S. Brassington, S. J. Coles, M. B. Hursthouse,
Inorg. Chem. Communications 2000, 3, 530.
D. C. Bradley, R. C. Mehrotra, D. P. Gaur, Metal Alkoxides,
Academic Press, 1978, London, England.
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
D. D. Devore, J. D. Lichtenhan, F. Takusagawa, E. A. Maatta,
J. Am. Chem. Soc. 1987, 109, 7408.
[19]
[20]
[21]
D. Rehder, Coordination Chemistry Reviews 1991, 110, 161.
W. Priebsch, D. Rehder, Inorg. Chem. 1985, 24, 3058.
H. Hagen, C. Bezemer, J. Boersma, H. Kooijman, M. Lutz, A.
Spek, G. Van Koten, Inorg. Chem. 2000, 39, 3970.
[1]
[1a] R. L. Halterman, in ‘‘Metallocenes’’; (Eds.: A. Togni; R. L.
Halterman);Wiley-VCH: New York, 1998, vol. 1, chapter 8, p.
[1b]
[22] [22a]
455. Some recent contributions:
N. E. Grimmer, N. J. Co-
R. Choukroun, P. Moumboko, S. Chevalier, M. Etienne,
[22b]
ville, C. B. De Koning, J. M. Smith, L. M Cook, J. Organomet.
B. Donnadieu, Angew. Chem. Int. Ed. 1998, 37, 3169.
C.
[1c]
Chem. 2000, 616, 112.
E. J. Thomas, M. D. Rausch, J. C.
Lorber, R. Choukroun, B. Donnadieu, Inorg. Chem. 2002, 41,
W. Chien, Organometallics 2000, 19, 5744. [1d] F. Zhang, Y. Mu,
L. Zhao, Y. Zhang, W. Bu, C. Chen, H. Zhai, H. Hong, J.
[22c]
4217.
R. Choukroun, F. Wolff, Unpublished results.
[23]
[24]
C. P. Gerlach, J. Arnold, Organometallics 1996, 15, 5260.
A. G. Massey, A. J. Park, J. Organomet. Chem. 1964, 21, 245.
Organomet. Chem. 2000, 613, 68. For some recent leading refer-
[1e]
[25] [25a] A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi,
ences see also:
1205.
A. Alt, H. G. Köppl, Chem. Rev. 2000, 100,
[1f]
[1g]
[25b]
G. W. Coates, Chem. Rev. 2000, 100, 1223.
G. G.
J. Appl. Crystallogr. 1993, 26, 343.
A. Altomare, M. C.
[1h]
Hlatky, Chem. Rev. 2000, 100, 1347.
E. Chen, T. J. Marks,
Burla, M. Camalli, G. L. Cascarano, C. Giacovazzo, A. Guag-
liardi, A. G. G. Moliterni, G. Polidori, R. Spagna, J. Appl.
Cryst. 1999, 32, 115.
Chem. Rev. 2000, 100, 1391. [1i] V. C. Britovsek, G. J. P. Gibson,
D. F. Wass, Angew. Chem. Int. Ed. 1999, 38, 428. [1j] W. E. Piers,
T. Chivers, Chem. Soc. Rev. 1997, 26, 345.
[26]
G. M. Sheldrick, SHELX97 (Includes SHELXS-97, SHELXL-
97, CIFTAB), Institüt für Anorganische Chemie der Univer-
sität, Tammanstrasse 4, Göttingen, Germany, 1998.
L. Farrugia, J. Appl. Crystallogr. 1999, 32, 837.
International Tables for X-ray Crystallography, vol. IV, Kynoch
Press, Birmingham, England, 1974.
[2] [2a]
G. J. Pindado, M. Thornton-Pett, M. Bouwkamp, A.
Meetsma, B. Hessen, M. Bochmann, Angew. Chem. Int. Ed.
Engl. 1997, 36, 2358. [2b] T. J. Woodman, M. Thornton-Pett, D.
L. Hughes, M. Bochmann, Organometallics 2001, 20, 4080.
R. Gomez, M. L. H. Green, J. L. J. Haggitt, J. Chem. Soc.,
[27]
[28]
[2c]
[2d]
[29]
Dalton Trans. 1996, 939.
J. Klosin, G. R. Roof, E. Y-X.
L. Farrugia, J. Appl. Crystallogr. 1997, 30, 565.
[2e]
Chen, K. A. Abboud, Organometallics 2000, 19, 4684.
D.
Received July 26, 2002
Bellamy, N. G Connelly, O. M. Hicks, A. G. Orpen, J. Chem.
[I02422]
632
Eur. J. Inorg. Chem. 2003, 628Ϫ632