Contrasting cyclo-P3 ligand transfer reactivity of valence-isoelectronic aryloxide complexes [(P3)Nb(ODipp) 3]- and [(P3)W(ODipp)3]

Article abstract of DOI:10.1002/ejic.201301140

Reduction of mer-Cl₃W(ODipp)₃ with Na/Hg in the presence of P₄ in toluene afforded the orange complex (η³-P₃)W(ODipp)₃ (δ31P = -156 ppm, 10-% isolated yield). Unlike the valence-isoelectron

Full text of DOI:10.1002/ejic.201301140

SHORT COMMUNICATION
DOI:10.1002/ejic.201301140
Contrasting cyclo-P3 Ligand Transfer Reactivity of
Valence-Isoelectronic Aryloxide Complexes
[(P3)Nb(ODipp)3]– and [(P3)W(ODipp)3]
CLUSTER
ISSUE
Jens M. Breunig,[a,b] Daniel Tofan,[a] and
Christopher C. Cummins*[a]
Keywords: Phosphorus / P4 activation / Tungsten / Ligand-transfer reactions / Transition metals
Reduction of mer-Cl3W(ODipp)3 with Na/Hg in the presence
of P4 in toluene afforded the orange complex (η3-P3)W-
the cyclo-P3 ligand to generate AsP3. Instead, this complex
underwent aryloxide ligand transfer to form the red complex
(ODipp)3 (δ
= –156 ppm, 10% isolated yield). Unlike the
(η3-P3)W(Cl)(ODipp)2(THF) (δ
31P
31P
= –143 ppm, 32% isolated
valence-isoelectronic anion [(η3-P3)Nb(ODipp)3]–, treatment
yield).
with AsCl3 of the neutral (η3-P3)W(ODipp)3 did not transfer
decided to expand the scope of reactions that might afford
the AsP3 molecule and became interested in investigating
the dependence of AsP3 formation in the absence of an an-
ionic charge by using the valence-isoelectronic, neutral
complex (η3-P3)W(ODipp)3 (1-W).
Introduction
Lately, the activation of white phosphorus has received
renewed interest from the research community in an effort
to develop green chemistry routes to value-added phos-
phorus-containing chemicals.[1] Although the maturing field
of coordination chemistry of P4 has begun to uncover path-
ways towards efficient access to such chemicals, examples
are still relatively rare.[1] A common route for functionaliz-
ing P4 has been to form cyclo-P3 complexes, as such com-
pounds have been structurally characterized for most met-
als in groups 5–10 (except group 7) and thorium.[2–12] How-
ever, other than the formation of multinuclear P3 com-
plexes, the functionalization of cyclo-P3 ligands has only
been reported for very few cases, such as in the formation
of η3-RP3 triphosphirene ligands[4,13] or P6 fragments.[5]
The [(η3-P3)Nb(ODipp)3]– anion ([1-Nb]–, Dipp = 2,6-
iPr2C6H3) is the only complex that has been reported to
yield products in which the P3 fragment is completely re-
moved from the transition metal center.[2,6] Treatment with
appropriate reagents allowed the transfer of the cyclo-P3
unit to form either polycyclic Ph3SnP3(C6H8)[6] or tetrahe-
dral AsP3.[2] While the former can be further employed for
a formal [P3]3– group transfer,[6] the latter has been shown
to exhibit a wide range of reactivity.[2,14] As a result, we
cyclo-P3 complexes have typically been synthesized by
treatment of P4 with precursors containing metals in low
oxidation states[7,8] or very labile ligands,[9,10,15] but they
have also been prepared from phosphorus-rich complexes
(with P4 ligands)[16] or from terminal metal phosphides
upon treatment with P2 sources.[11,12] There have been, how-
ever, only three examples of structurally characterized η3-
P3 complexes bearing aryloxide or alkoxide ligands.[2,7,10]
Neutral complex (η3-P3)W(OCH2tBu)3(HNMe2) has been
prepared by the treatment of W2(OCH2tBu)6(HNMe2)2
with P4 in 30% yield,[7] while (η3-P3)Mo(OCy)3(HN[iPr]Ar)
(Cy = cyclohexyl, Ar = 3,5-Me2C6H3) has been isolated in
41% yield by the treatment of (η3-P3)Mo(N[iPr]Ar)3 with
cyclohexanol.[10] Anionic complex [1-Nb]– was synthesized
in a single step by the reduction of Cl2Nb(ODipp)3 with
Na/Hg in the presence of P4 in 57% yield.[2] Of these three
complexes, only the reactivity of the niobium complex has
been investigated.[2,6] We report here the synthesis of neutral
tungsten complex 1-W by reduction of complex Cl3W-
(ODipp)3 in the presence of P4, as well as the strikingly
contrasting reactivity with AsCl3 that we observe for the
valence-isoelectronic complexes [(P3)M(ODipp)3]n– (M =
Nb, n = 1; M = W, n = 0).
[a] Massachusetts Institute of Technology, Department of
Chemistry,
77 Massachusetts Avenue, Cambridge, Massachusetts 02139,
USA
E-mail: ccummins@mit.edu
http://web.mit.edu/ccclab/
Results and Discussion
[b] Institut für Anorganische Chemie, Goethe-Universität
Frankfurt am Main,
The published synthesis of mer-Cl3W(ODipp)3 by heat-
ing WCl6 and HODipp at reflux involves tedious column
chromatography to purify the desired product.[17] We have
Max-von-Laue-Straße 7, 60438 Frankfurt am Main, Germany
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201301140.
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SHORT COMMUNICATION
been able to scale up this protocol and simplify the purifica-
X-ray-quality crystals of (η3-P3)W(ODipp)3 were grown
tion procedure by simply recrystallizing the product from from a concentrated diethyl ether solution at –35 °C. The
hexane at –35 °C to afford a yield of 61% (16 g). Reduction solid-state structure of 1-W (Figure 1) is very similar to that
of this mer-Cl3W(ODipp)3 complex with a mild reducing of the previously reported anion [1-Nb]–.[2] The W–P dis-
agent such as zinc powder stopped at the tungsten(V) com- tances [2.4389(7)–2.4471(7) Å] are approximately 0.08 Å
plex. Theparamagnetic, orange-redcomplex Cl2W(ODipp)3- shorter than the Nb–P ones, corresponding to a decrease in
(THF) could be recrystallized from diethyl ether at –35 °C the covalent radii of tungsten compared to those of ni-
in 82% yield and was observed to be isostructural to the obium (1.37 Å vs. 1.47 Å[21]). The P–P bonds in 1-W
precursor for the [1-Nb]– anion,[2] only differing in the Cl– [2.174(1)–2.180(1) Å] are also shorter by about 0.02 Å rela-
M–Cl angles: 174.02(2)° for tungsten (Figure S1) and tive to those in [1-Nb]–. Complex 1-W exhibits shorter W–
162.41(4)° for niobium.
P distances (ca. 0.05 Å) and longer P–P distances (ca.
Since formation of [1-Nb]– had been found to proceed 0.022 Å) relative to tungsten complex (η3-P3)W(OCH2tBu)3-
most efficiently when sodium amalgam was used as the re- (HNMe2).[7]
ducing agent in the presence of P4, the same conditions
were tested with the mer-Cl3W(ODipp)3 precursor. How-
ever, a cyclo-P3 product could not be obtained by means of
a Na/Hg reduction in the presence of P4 in THF. Only upon
changing the solvent to toluene could the formation of the
neutral 1-W complex be observed. Stirring Cl3W(ODipp)3
in the presence of P4 and excess Na/Hg (0.7%) led to the
formation of an orange-red mixture within 10 min, consis-
tent with the formation of a tungsten(V) species (Scheme 1).
Continued stirring led to a black mixture within 30 min,
but complete consumption of the tungsten(VI) precursor
was only observed after 3.5 h (1H NMR spectroscopy).
Figure 1. Solid-state structure (left) and 31P NMR signal (right,
31
1J183
= 9 Hz) of (η3-P3)W(ODipp)3 (1-W). Thermal ellipsoids
W
P
are shown at the 50% probability level, and hydrogen atoms are
omitted for clarity. Selected bond lengths [Å] and angles [°]: P1–P2
2.1742(10), P1–P3 2.1804(10), P2–P3 2.1789(10), W1–P1 2.4471(7),
W1–P2 2.4460(7), W1–P3 2.4389(7); P1–P2–P3 60.12(3), P2–P1–
P3 60.05(3), P2–P3–P1 59.84(3), P1–W1–P2 52.76(2), P1–W1–P3
53.01(2), P2–W1–P3 52.98(2), P1–P2–W1 63.64(3).
Treatment of 1-W with either PCl3 or AsCl3 in THF led
to very slow reactivity and no observable EP3 formation (E
= P, As). These observations stand in stark contrast to
those obtained under similar conditions with [1-Nb]–, where
complete conversion to AsP3 was observed within 30 min
Scheme 1. Synthesis of (η3-P3)W(ODipp)3 (1-W) and reactivity
with AsCl3.
After repeated attempts, the isolated yield of 1-W could after the addition of one equivalent of AsCl3.[2] Reaction of
only be optimized to 10%. This is likely due to an unselec- 1-W with either PCl3 or AsCl3 led to the same new metal
tive reductive process. Indeed, a side-product consistent complex. The reaction of 1-W with AsCl3 was observed to
with this was identified as the previously reported complex be qualitatively faster than that with PCl3. However, in the
W(ODipp)4.[18] Ligand exchange reactions for tungsten presence of one equivalent of AsCl3 only a very small
complexes with aryloxide or alkoxide ligands are well amount of 1-W was converted to this new product after
known,[19] but for niobium complexes such behavior has 45 min. A small amount of 1-W was still present after 26 h
been reported exclusively for homoleptic complexes.[20] of stirring in the presence of 2.6 equiv. of AsCl3 in THF.
These observations seem to suggest a greater lability of the The new metal-containing product was identified as (η3-
ODipp ligand under reducing conditions in the presence of P3)W(Cl)(ODipp)2(THF) by X-ray diffraction (Figure 2). It
alkali metal ions for tungsten as compared with niobium.
could be isolated as red crystals in 32% yield by cooling a
The 1H NMR spectrum of 1-W reveals a single aryloxide concentrated diethyl ether solution at –35 °C. In the solid
environment with a doublet-septuplet aliphatic pair and state, the W–P distances [2.4801(10)–2.4888(10) Å] are elon-
two aromatic multiplets. It exhibits a sharp 31P NMR signal gated by about 0.04 Å with respect to those found in 1-W,
at δ = –156 ppm, with tungsten-183 satellites (1J
=
probably a result of the higher coordination number around
183W31
P
9 Hz). These data are similar to those reported for (η3-P3)- the tungsten atom. This, in turn, leads to a slight contrac-
W(OCH2tBu)3(HNMe2) (δ = –205 ppm, 16 Hz).[7]
tion in the P–P distances [2.1460(15)–2.1540(15) Å] by
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SHORT COMMUNICATION
about 0.03 Å. The 31P NMR spectrum of (η3-P3)W(Cl)-
(ODipp)2(THF) has only one broad resonance at –143 ppm
(Δν1/2 = 413 Hz), which can be explained by the low sym-
metry of the complex.
Experimental Section
Methods: All manipulations were performed under a dry N2 atmo-
sphere, inside a glovebox, or by using a Schlenk line. Solvents were
obtained anhydrous and oxygen-free. [D6]Benzene was acquired
from Cambridge Isotope Laboratories, dried with Na/benzo-
phenone, and distilled prior to use. White phosphorus was acquired
from ThermPhos International. NMR spectra were obtained with
Varian Mercury 300 or Bruker Avance-400 instruments equipped
with SpectroSpin or Magnex Scientific superconducting magnets,
and the signals were referenced to appropriate solvent reso-
nances.[23] 31P NMR spectra were referenced externally against 85%
H3PO4 (δ31 = 0 ppm).
P
(η3-P3)W(ODipp)3 (1-W): A sample of Na (0.168 g, 7.31 mmol,
6 equiv.) was added to a sample of Hg (24 g) and the 0.7% amal-
gam was cooled to room temperature. A P4 (0.182 g, 1.47 mmol,
1.2 equiv.) and mer-Cl3W(ODipp)3 (1.006 g, 1.22 mmol, 1 equiv.)
solution in toluene (90 mL) was added to the Na amalgam, and
the mixture was stirred vigorously at room temperature for 3.5 h.
This was then filtered through a plug of Celite, and the residues
were washed with toluene (3ϫ 20 mL). Volatiles from the red fil-
trate were removed under reduced pressure, and the orange residue
was dissolved in pentane (50 mL), filtered, and dried to yield the
crude product (181 mg). This was redissolved in pentane (20 mL),
and the solution was stored at –35 °C overnight. The resulting
orange crystalline solid was collected on a fritted glass filter,
washed with thawing pentane (20 mL), and dried to yield analyti-
cally pure 1-W (96 mg, 0.12 mmol, 10% yield). X-ray quality crys-
tals were grown at –35 °C from a concentrated diethyl ether solu-
Figure 2. Solid-state structure of (η3-P3)W(Cl)(ODipp)2(THF) with
thermal ellipsoids at the 50% probability level and hydrogen atoms
omitted for clarity. Selected bond lengths [Å] and angles [°]: P1–P2
2.1460(15), P1–P3 2.1519(14), P2–P3 2.1540(15), W1–P3
2.4801(10), W1–P1 2.4818(10), W1–P2 2.4888(10); P2–P1–P3
60.16(5), P1–P2–P3 60.06(5), P1–P3–P2 59.78(5), P3–W1–P1
51.40(3), P3–W1–P2 51.38(3), P1–W1–P2 51.16(4).
It is likely that, for the [1-Nb]– anion, fast reactivity with
group 15 element halides was favored by salt metathesis –
as was shown to be the case when treatment with Ph3SnCl
yielded dinuclear complex Ph3Sn(η1:2-P3)Nb(ODipp)3.[6] In
contrast, neutral complex 1-W does not provide for such a
thermodynamic sink and a fast initial step. This result is
consistent with other aryloxide or alkoxide ligand exchange
reactions observed upon treatment of neutral transition
metal complexes with main-group halides.[22]
1
tion. H NMR (300 MHz, [D6]benzene, 20 °C): δ = 7.13 (m, 6 H),
3
3
7.00 (m, 3 H), 3.42 (sept, JHH = 6.8 Hz, 6 H), 1.26 (d, JHH
=
6.8 Hz, 36 H) ppm. 13C NMR (101 MHz, [D6]benzene, 20 °C): δ =
157.7, 139.7, 125.9, 124.0, 27.4, 24.5 ppm. 31P NMR (121 MHz,
1
183W31
P
[D6]benzene, 20 °C): δ = –156.4 (Δν1/2 = 2.1 Hz; J
= 9 Hz)
ppm. C36H51O3P3W (808.55): calcd. C 53.48, H 6.36; found C
53.06, H 6.15.
(η3-P3)W(Cl)(ODipp)2(THF): Caution: AsCl3 is highly toxic and
should be handled with the utmost care! AsCl3 (35 mg, 0.19 mmol,
2.6 equiv.) from a THF stock solution was diluted in THF (3 mL),
while 1-W (60 mg, 0.07 mmol, 1 equiv.) was dissolved in THF
(2 mL). The just-thawed AsCl3 solution was added to the thawing
1-W solution. The reaction mixture was warmed up to room tem-
perature and stirred for 26 h, after which all volatiles were removed
under reduced pressure. The resulting residue was redissolved in
pentane (8 mL) and then stored at –35 °C. The red crystalline solids
were collected on a fritted glass filter and washed with thawing
pentane (1 mL) to yield analytically pure (η3-P3)W(Cl)(ODipp)2-
(THF) (18 mg, 0.024 mmol, 32% yield). X-ray quality crystals were
grown out of a concentrated diethyl ether solution at –35 °C. 1H
Conclusions
The present work was motivated by a desire to under-
stand the factors that enable efficient transfer of a cyclo-P3
ligand to main-group acceptors when using the negatively
charged complex [1-Nb]–. The present study of the valence-
isoelectronic neutral complex 1-W containing niobium’s di-
agonal relative element, tungsten, gave only evidence for
halide/aryloxide ligand exchange upon treatment with ECl3
(E = P, As), tempting us to speculate that the possibility
for salt elimination (i.e., formation of a NaCl precipitate)
together with the negative charge in the niobium system
may make the cyclo-P3 ligand respectively faster-reacting
and more nucleophilic in the niobium system. Alternatively,
the bonding in the MP3 tetrahedron may be more covalent
for tungsten (or molybdenum) than for niobium, thus en-
abling ancillary ligand exchange reactions to occur without
disturbing the MP3 unit. Studies of neutral niobium cyclo-
P3 complexes would be an interesting undertaking to fur-
ther unravel the requirements for successful P3-ligand func-
tionalization and transfer reactivity.
3
NMR (400 MHz, [D6]benzene, 20 °C): δ = 7.23 (d, JHH = 7.7 Hz,
3
3
4 H), 7.05 (t, JHH = 7.7 Hz, 2 H), 4.10 (m, 4 H), 3.35 (sept, JHH
= 6.8 Hz, 4 H), 1.35 (m, 16 H), 1.28 (d, 3JHH = 6.8 Hz, 12 H) ppm.
13C NMR (101 MHz, [D6]benzene, 20 °C): δ = 159.0, 137.7, 125.9,
123.9, 71.2, 27.5, 25.5, 24.5, 23.8, 22.7 ppm. 31P NMR (162 MHz,
[D6]benzene, 20 °C):
δ = –142.7 (Δν1/2 = 413 Hz) ppm.
C28H42ClO3P3W (738.85): calcd. C 45.52, H 5.73; found C 45.33,
H 5.69.
X-ray Crystal Structure Analysis: Crystals were mounted in hydro-
carbon oil on a nylon loop and diffraction data were collected at
100 K on a Siemens platform three-circle diffractometer coupled to
a Bruker-AXS Smart Apex CCD detector with graphite-monochro-
matized Mo-Kα radiation (λ = 0.71073 Å) performing φ and ω
scans. General refinement details are discussed elsewhere.[24]
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SHORT COMMUNICATION
[3]
a) E. B. Hulley, P. T. Wolczanski, E. B. Lobkovsky, Chem.
Commun. 2009, 6412–6414; b) B. L. Tran, M. Singhal, H. Park,
O. P. Lam, M. Pink, J. Krzystek, A. Ozarowski, J. Telser, K.
Meyer, D. J. Mindiola, Angew. Chem. 2010, 122, 10067; Angew.
Chem. Int. Ed. 2010, 49, 9871–9875; c) H. A. Spinney, N. A.
Piro, C. C. Cummins, J. Am. Chem. Soc. 2009, 131, 16233–
16243; d) S. Welsch, M. Bodensteiner, M. Dusek, M. Sierka,
M. Scheer, Chem. Eur. J. 2010, 16, 13041–13045; e) L.
Yoong Goh, C. K. Chu, R. C. S. Wong, J. Chem. Soc., Dalton
Trans. 1989, 1951–1956; f) R. Ahlrichs, D. Fenske, K. Fromm,
H. Krautscheid, U. Krautscheid, O. Treutler, Chem. Eur. J.
1996, 2, 238–244; g) P. Barbaro, M. Di Vaira, M. Peruzzini, S.
Seniori Constantini, P. Stoppioni, Eur. J. Inorg. Chem. 2005,
1360–1368; h) C. Bianchini, M. Di Vaira, A. Meli, L. Sacconi,
Inorg. Chem. 1981, 20, 1169–1173; i) C. Bianchini, M. Di Vaira,
A. Meli, L. Sacconi, J. Am. Chem. Soc. 1981, 103, 1448–1452;
j) M. Di Vaira, M. P. Ehses, M. Peruzzini, P. Stoppioni, Polyhe-
dron 1999, 18, 2331–2336; k) M. Di Vaira, M. P. Ehses, P. Stop-
pioni, Inorg. Chem. 2000, 39, 2199–2205; l) M. Di Vaira, C. A.
Ghilardi, S. Midollini, L. Sacconi, J. Am. Chem. Soc. 1978,
100, 2550–2551; m) M. Di Vaira, D. Rovai, P. Stoppioni, Poly-
hedron 1990, 9, 2477–2481; n) M. Di Vaira, P. Stoppioni, M.
Peruzzini, J. Chem. Soc., Dalton Trans. 1990, 109–113; o) P.
Dapporto, L. Sacconi, P. Stoppioni, F. Zanobini, Inorg. Chem.
1981, 20, 3834–3839; p) O. J. Scherer, B. Werner, G. Heckmann,
G. Wolmershauser, Angew. Chem. 1991, 103, 562; Angew.
Chem. Int. Ed. Engl. 1991, 30, 553–555.
M. Di Vaira, P. Stoppioni, S. Midollini, F. Laschi, P. Zanello,
Polyhedron 1991, 10, 2123–2129.
a) M. Di Vaira, P. Stoppioni, Polyhedron 1994, 13, 3045–3051;
b) E. B. Hulley, P. T. Wolczanski, E. B. Lobkovsky, Chem.
Commun. 2009, 42, 6412–6414.
B. M. Cossairt, C. C. Cummins, Angew. Chem. 2010, 122, 1639;
Angew. Chem. Int. Ed. 2010, 49, 1595–1598.
M. H. Chisholm, J. C. Huffman, J. W. Pasterczyk, Inorg. Chim.
Acta 1987, 133, 17–18.
M. Di Vaira, L. Sacconi, P. Stoppioni, J. Organomet. Chem.
1983, 250, 183–195.
M. Scheer, G. Friedrich, K. Schuster, Angew. Chem. 1993, 105,
641–643; Angew. Chem. Int. Ed. Engl. 1993, 32, 593–594.
F. H. Stephens, M. J. A. Johnson, C. C. Cummins, O. P. Krya-
tova, S. V. Kryatov, E. V. Rybak-Akimova, J. E. McDonough,
C. D. Hoff, J. Am. Chem. Soc. 2005, 127, 15191–15200.
N. A. Piro, C. C. Cummins, J. Am. Chem. Soc. 2008, 130, 9524–
9535.
Crystal Data for Cl2W(ODipp)3(THF): C40H59Cl2O4W, monoclinic,
P21/n space group, a = 10.4827(6) Å, b = 23.1828(14) Å, c =
16.5126(10) Å, β = 95.8970(10)°, V = 3991.6(4) Å3, Z = 4, ρcalcd.
=
1.429 gcm–3, μ = 3.065 mm–1. A total of 88816 reflections were
collected in the 2θ range of 1.52–29.57°, 11194 being unique (Rint
= 0.0541). An analytical absorption correction was applied on the
basis of the intensities of equivalent reflections (Tmin = 0.5628, Tmax
= 0.7461). Least-squares refinement on 436 parameters converged
normally with R1 [IϾ2σ(I)] = 0.0248, wR2 = 0.0587, GOOF =
1.062.
Crystal Data for (η3-P3)W(ODipp)3: C36H51O3P3W, monoclinic,
P21/n space group, a = 10.6955(9) Å, b = 17.2654(14) Å, c =
20.4942(16) Å, β = 103.4440(10)°, V = 3680.8(5) Å3, Z = 4, ρcalcd.
= 1.459 gcm–3, μ = 3.301 mm–1. A total of 84532 reflections were
collected in the 2θ range of 2.31–27.47°, 8453 being unique (Rint
=
0.0530). An analytical absorption correction was applied on the
basis of the intensities of equivalent reflections (Tmin = 0.5728, Tmax
= 0.8018). Least-squares refinement on 400 parameters converged
normally with R1 [IϾ2σ(I)] = 0.0219, wR2 = 0.0532, GOOF =
1.076.
Crystal
Data
for
(η3-P3)W(Cl)(ODipp)2(THF)·½THF:
¯
C30H46ClO3.5P3W, triclinic, P space group, a = 9.6030(11) Å, b =
13.6166(16) Å, c = 14.0563(16) Å, α = 110.625(2)°, β = 103.335(2)°,
γ = 91.693(2)°, V = 1661.4(3) Å3, Z = 2, ρcalcd. = 1.549 gcm–3, μ =
3.731 mm–1. A total of 36833 reflections were collected in the 2θ
range of 1.60–29.57°, 9231 being unique (Rint = 0.0449). An analyt-
ical absorption correction was applied on the basis of the intensities
of equivalent reflections (Tmin = 0.5519, Tmax = 0.7461). Least-
squares refinement on 424 parameters converged normally with R1
[IϾ2σ(I)] = 0.0362, wR2 = 0.0985, GOOF = 1.075. The bound
THF was disordered over two positions with occupancies refined
freely, and their sum was restrained to unity. The free THF was
disordered over two symmetry-related positions with occupancies
restrained to ½.
[4]
[5]
[6]
[7]
[8]
[9]
[10]
CCDC-954448 [for Cl2W(ODipp)3(THF)], -954449 [for (η3-P3)-
W(ODipp)3], and -954450 [for (η3-P3)W(Cl)(ODipp)2(THF)·
½THF] contain the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
[11]
[12]
[13]
D. Tofan, B. M. Cossairt, C. C. Cummins, Inorg. Chem. 2011,
50, 12349–12358.
Supporting Information (see footnote on the first page of this arti-
cle): Solid-state structure of Cl2W(ODipp)3(THF), optimized pro-
tocols for mer-Cl3W(ODipp)3 and Cl2W(ODipp)3(THF), and com-
plete NMR spectroscopic details for all compounds.
a) A. Barth, G. Huttner, M. Fritz, L. Zsolnai, Angew. Chem.
1990, 102, 956–958; Angew. Chem. Int. Ed. Engl. 1990, 29, 929–
931; b) S. Beyreuther, J. Hunger, G. Huttner, S. Mann, L. Zsol-
nai, Chem. Ber. 1996, 129, 745–757; c) G. Capozzi, L. Chiti,
M. Di Vaira, M. Peruzzini, P. Stoppioni, J. Chem. Soc., Chem.
Commun. 1986, 1799–1800.
a) B. M. Cossairt, C. C. Cummins, J. Am. Chem. Soc. 2009,
131, 15501–15511; b) B. M. Cossairt, C. C. Cummins, Chem.
Eur. J. 2010, 16, 12603–12608.
a) C. Bianchini, C. Mealli, A. Meli, L. Sacconi, Inorg. Chim.
Acta 1979, 37, L543–L544; b) C. A. Ghilardi, S. Midollini, A.
Orlandini, L. Sacconi, Inorg. Chem. 1980, 19, 301–306; c) T.
Gröer, M. Scheer, Z. Anorg. Allg. Chem. 2000, 626, 1211–1216;
d) O. J. Scherer, T. Dave, J. Braun, G. Wolmershäuser, J. Or-
ganomet. Chem. 1988, 350, C20–C24.
Acknowledgments
[14]
[15]
This work is based upon work supported by the US National Sci-
ence Foundation under CHE-1111357. J. M. B. acknowledges fin-
ancial support by the German Academic Exchange Service and the
German National Academic Foundation, and support from Prof.
Matthias Wagner. We thank Brandi M. Cossairt and Christopher
R. Clough for help with synthesis and crystallography.
[16]
a) M. Scheer, S. Deng, O. J. Scherer, M. Sierka, Angew. Chem.
2005, 117, 3821; Angew. Chem. Int. Ed. 2005, 44, 3755–3758;
b) M. Peruzzini, J. A. Ramirez, F. Vizza, Angew. Chem. 1998,
110, 2376; Angew. Chem. Int. Ed. 1998, 37, 2255–2257.
F. Quignard, M. Leconte, J. M. Basset, L. Y. Hsu, J. J. Alexan-
der, S. G. Shore, Inorg. Chem. 1987, 26, 4272–4277.
M. L. Listemann, R. R. Schrock, J. C. Dewan, R. M. Kolod-
ziej, Inorg. Chem. 1988, 27, 264–271.
[1] a) M. Caporali, L. Gonsalvi, A. Rossin, M. Peruzzini, Chem.
Rev. 2010, 110, 4178–4235; b) B. M. Cossairt, N. A. Piro, C. C.
Cummins, Chem. Rev. 2010, 110, 4164–4177; c) M. Scheer, G.
Balázs, A. Seitz, Chem. Rev. 2010, 110, 4236–4256; d) C. D.
Martin, C. M. Weinstein, C. E. Moore, A. L. Rheingoldb, G.
Bertrand, Chem. Commun. 2013, 49, 4486–4488.
[17]
[18]
[2] B. M. Cossairt, M.-C. Diawara, C. C. Cummins, Science 2009,
323, 602.
Eur. J. Inorg. Chem. 2014, 1605–1609
1608
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.eurjic.org
SHORT COMMUNICATION
[19] a) A. Lehtonen, R. Sillanpää, Polyhedron 2000, 19, 2579–2584;
b) A. Lehtonen, R. Sillanpää, Inorg. Chem. 2001, 40, 6047–
6051; c) A. Lehtonen, R. Sillanpää, Polyhedron 2002, 21, 1017–
1022; d) A. Lehtonen, R. Sillanpää, Polyhedron 2003, 22, 2755–
2760; e) M. R. Churchill, Y.-J. Li, K. H. Theopold, R. R.
Schrock, Inorg. Chem. 1984, 23, 4472–4476.
[20] a) S. Lim, J. C. Lee, D. S. Sohn, W. I. Lee, I.-M. Lee, Chem.
Mater. 2002, 14, 1548–1554; b) M. K. Sharma, A. Singh, R. C.
Mehrotra, Transition Met. Chem. 2002, 27, 115–119.
[21] P. Pyykkö, M. Atsumi, Chem. Eur. J. 2009, 15, 186–197.
[22] a) V. Cadierno, M. Zablocka, B. Donnadieu, A. Igau, J.-P. Ma-
joral, A. Skowronska, Chem. Eur. J. 2001, 7, 221–229; b) A.
Fischbach, F. Perdih, E. Herdtweck, R. Anwander, Organome-
tallics 2006, 25, 1626–1642; c) J. J. Doney, R. G. Bergman,
C. H. Heathcock, J. Am. Chem. Soc. 1985, 107, 3724–3726; d)
N. Steiner, E. Ehrenstorfer, J. Chen, W. Beck, Chem. Ber. 1988,
121, 275–279; e) D. J. Krysan, P. B. Mackenzie, J. Am. Chem.
Soc. 1988, 110, 6273–6274; f) S. Roelens, J. Chem. Soc. Perkin
Trans. 2 1988, 2105–2110; g) H. Yasuda, H. Yamamoto, K.
Yokota, A. Nakamura, Chem. Lett. 1989, 7, 1309–1312; h) J.
Christoffers, R. G. Bergman, Angew. Chem. 1995, 107, 2423;
Angew. Chem. Int. Ed. Engl. 1995, 34, 2266–2267; i) T. Braun,
S. Rothfeld, V. Schorlemer, A. Stammler, H.-G. Stammler, In-
org. Chem. Commun. 2003, 6, 752–755; j) S. Ogoshi, K. Tono-
mori, M. Oka, H. Kurosawa, J. Am. Chem. Soc. 2006, 128,
7077–7086.
[23] G. R. Fulmer, A. J. M. Miller, N. H. Sherden, H. E. Gottlieb,
A. Nudelman, B. M. Stoltz, J. E. Bercaw, K. I. Goldberg, Orga-
nometallics 2010, 29, 2176–2179.
[24] D. Tofan, C. C. Cummins, Chem. Sci. 2012, 3, 2474–2478.
Received: September 3, 2013
Published Online: October 30, 2013
Eur. J. Inorg. Chem. 2014, 1605–1609
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