Activation of a 1-chlorophosphirane complex by aluminum trichloride: Generation and trapping of [Fc-P-W(CO)5] (Fc = Ferrocenyl)

Article abstract of DOI:10.1002/ejic.201402662

Aluminum trichloride catalyzes the ring opening of a 1-chlorophosphirane W(CO)₅ complex and its reaction with thiophene and ferrocene to give the corresponding 1-(2-thienyl)- and 1-ferrocenylphosphirane derivatives. The W(CO)₅ complex of the 1-ferrocenylphosphirane is an efficient precursor of the phosphinidene complex [FcP-W(CO)₅], which is trapped by tolan, trans-stilbene, and water.

Full text of DOI:10.1002/ejic.201402662

SHORT COMMUNICATION
DOI:10.1002/ejic.201402662
Activation of a 1-Chlorophosphirane Complex by
Aluminum Trichloride: Generation and Trapping of
[Fc-P-W(CO)5] (Fc = Ferrocenyl)
Feny Ho,[a] Rakesh Ganguly,[a] and François Mathey*[a]
Keywords: Lewis acids / Sandwich complexes / Phosphiranes / Phosphorus / Tungsten
Aluminum trichloride catalyzes the ring opening of a 1-
chlorophosphirane W(CO)5 complex and its reaction with
thiophene and ferrocene to give the corresponding 1-(2-thi-
enyl)- and 1-ferrocenylphosphirane derivatives. The W(CO)5
complex of the 1-ferrocenylphosphirane is an efficient pre-
cursor of the phosphinidene complex [FcP-W(CO)5], which is
trapped by tolan, trans-stilbene, and water.
is practically not affected. Notably, the Al···Cl interaction
is loose (2.479 vs. 2.107–2.123 Å for normal Al–Cl bonds).
The difference between the energies of 2 and its two compo-
nents 1+AlCl3 indeed indicates a dissociation energy of
only 0.3 kcalmol–1 for this interaction. This means that, un-
der practical experimental conditions, there will be an equi-
librium between 2 and 1+AlCl3 that will be shifted toward
2 by an excess amount of aluminum chloride. Also signifi-
Introduction
Several methods have been described in the literature for
the synthesis of 1-chlorophosphiranes either as free species
or as P-W(CO)5 complexes.[1–7] These species have been al-
lowed to react with a variety of nucleophiles (Nu–) to give
the corresponding P–Nu phosphiranes. However, their reac-
tions with strong Lewis acids have been left untouched ex-
cept for one case in which a Cl-to-Me intramolecular ex-
change between phosphorus and silicon in a 1-chloro-2-tri-
methylsilylphosphirane was promoted by AlCl3.[2] The re-
cent availability of a transient chlorophosphinidene com-
plex [ClP-W(CO)5][7] has given us ready access to 1-chloro-
phosphirane complexes by reaction with alkenes. This has
prompted us to investigate more closely their reactions with
strong Lewis acids such as AlCl3.
–
cant is the fact that the fully ionized system P+ +AlCl4 is
82 kcalmol–1 higher in energy than 2. The full ionization of
the P–Cl bond is thus excluded.
Results and Discussion
To have an idea of what could be expected, we first de-
cided to investigate the interaction of 1-chlorophosphirane-
pentacarbonyltungsten complex 1 with AlCl3 by DFT at
the B3LYP/6-31G(d)-Lanl2dz(W) level.[8] The computed
structure of 1 is shown in Figure 1. Good agreement with
the X-ray crystal structure[4] is observed. Optimization of
the 1-AlCl3 system leads to loose complex 2 in which AlCl3
interacts with the chlorine atom of 1 (Figure 2). Compari-
son of the structures of 1 and 2 leads to some interesting
conclusions. The P–Cl bond is weakened by interaction
with AlCl3, and its length increases from 2.092 to 2.216 Å.
On the contrary, the structure of the phosphirane ring itself
Figure 1. Computed structure of 1-chlorophosphirane complex 1.
Main distances [Å] and angles [°]: P8–W19 2.512, P8–Cl7 2.092,
P8–C1 1.838; C1–P8–C2 48.96, Cl7–P8–C1 103.62, C1–P8–W19
129.56, Cl7–P8–W19 120.59.
Figure 2. Computed structure of AlCl3–phosphirane loose complex
2. Main distances [Å] and angles [°]: P–W 2.469, P–Cl 2.216, P–C
1.831, Cl···Al 2.479, Al–Cl 2.107–2.120–2.123; C–P–C 49.21, Cl–
P–C 103.79, W–P–C 133.96, W–P–Cl 115.71; P–Cl–Al 121.88; Cl–
Al–Cl 115.07–118.24–117.68.
[a] Nanyang Technological University, Division of Chemistry &
Biological Chemistry,
21 Nanyang Link, 637371 Singapore
E-mail: fmathey@ntu.edu.sg
www.spms.ntu.edu.sg/cbc
We selected 7-chloro-7-phosphabicyclo[4.1.0]heptane
complex 3 for our experiments because it is obtained as an
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201402662.
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SHORT COMMUNICATION
almost pure diastereomer by reaction of cyclohexene with thienyl. In both 3[7] and 5, the tungsten complexing group
[ClP-W(CO)5].[7] We immediately noticed that 3 slowly de- faces the cyclohexane ring. Owing to steric congestion re-
composes in the presence of AlCl3 contaminated by HCl sulting from interaction between the W(CO)5 complexing
[Equation (1)].
group and the six-membered ring, we could expect that 5
and 6 are potential precursors of [ArP-W(CO)5]. In the case
of 6, this possibility was quite exciting, as it is impossible
to use the classical 7-phosphanorbornadiene route to ob-
tain [FcP-W(CO)5] because the bulkiness of the ferrocenyl
group prevents cycloaddition between the 1-ferrocenylphos-
phole complex and dimethyl acetylenedicarboxylate.[11] We
(1)
We were unable to get good crystals of 4, but its identity tested our hypothesis by using diphenylacetylene, trans-stil-
was established as follows. The 31P NMR spectrum [4: bene, and water as the trapping reagents [Equation (3)].
1
δ(31P) = 162.9 ppm, JPW = 320.8 Hz] shows that the phos-
phirane ring has been opened. The 13C NMR spectrum
shows one CH at δ = 57.19 ppm (JCP = 5 Hz) and three
different CH2 groups at δ = 25.75 (s), 26.18 (JCP = 15 Hz),
and 26.97 ppm (JCP = 2.5 Hz). HRMS indicates that the
formula is C11H11O5PCl2W (calcd. 507.9230; found
507.9223). Finally, the identity of 4 was confirmed by com-
parison with another sample made by reaction of [Cl3P-
W(CO)5] with cyclohexylmagnesium bromide. It is known
that chlorophosphirane complexes are stable in the presence
of HCl (see the synthesis of the parent chlorophosphirane
tungsten complex[9]), but it appears that AlCl3 catalyzes
their ring opening. From a practical standpoint, conse-
quently, the reaction of 3 with electron-rich arenes in the
presence of AlCl3 must be faster than ring opening by HCl,
the presence of which cannot be avoided completely. Anis-
ole and furan were not reactive enough, but we were suc-
cessful with thiophene and ferrocene [Equation (2)]. We
think that the failures with furan and anisole are due to
complexation of AlCl3 with the oxygen atoms. This com-
plexation is quite strong with furan (14.7 kcalmol–1)[10] and
probably prevents the formation of the complex with the
chlorophosphirane. The complexation of AlCl3 with thio-
phene (8.5 kcalmol–1)[10] is much weaker and does not in-
terfere with the reaction at P–Cl.
Figure 3. X-ray crystal structure of 5. Main distances [Å] and
angles [°]: P1–W1 2.5078(9), P1–C6 1.803(4), P1–C10 1.841(4), P1–
C11 1.849(4), C6–S1 1.724(4), C9–S1 1.718(4), C6–C7 1.370(5),
C7–C8 1.418(6), C8–C9 1.348(6), C10–C11 1.520(5); C10–P1–C11
48.64(17), C10–P1–C6 102.75(17), C11–P1–C6 105.43(17), C6P1–
W1 116.83(12).
(2)
The X-ray crystal structure of 5 is shown in Figure 3.
Phosphirene 9 has already been described in the litera-
The key observation is that the stereochemistry of phos- ture.[12] The molecular structure of new phosphirane 8 was
phorus has been kept during the substitution of chlorine by confirmed by X-ray crystal structure analysis (Figure 4).
(3)
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SHORT COMMUNICATION
of-plane angle is 18.4°. The HOMO–LUMO gap at 2.51 eV
is larger than that for [MeP-W(CO)5] at 2.34 eV. From this
standpoint, 7 lies between the C-substituted phosphinidene
complex and the less-electrophilic N-substituted phosphin-
idene complex.[15] From another standpoint, it is quite
interesting to compare the reactions of the 1-chlorophos-
phirane and 1-chlorophosphirene complexes with AlCl3. In
the second case, full ionization of the P–Cl bond takes
place, which leads to the aromatic phosphirenylium ion, as
shown by Sterenberg.[12]
Conclusions
The most useful result of this work is that complex 3,
due to its congested structure, is a potential source of new
terminal phosphinidene complexes [RP-W(CO)5] of wide
synthetic interest.
Figure 4. X-ray crystal structure of 8. Main distances [Å] and
angles [°]: P1–W1 2.5012(9), P1–C6 1.849(3), P1–C7 1.835(3), P1–
C20 1.797(3), C6–C7 1.523(5), Fe1–C20–24 2.038–2.046(4), Fe1–
C25–29 2.030–2.044(4); C6–P1–C7 48.84(15), C6–P1–W1
125.80(11), C7–P1–W1 121.34(11), C6–P1–C20 105.87(15), C7–P1–
C20 109.64(15), C20–P1–W1123.07(11).
Experimental Section
General Methods: All reactions were performed with distilled dry
solvents. Silica gel (230–400 mesh) was used for chromatographic
separations. NMR spectra were recorded with a Bruker BBFO
400 MHz, AV 400 MHz, or AV 500 MHz spectrometer. All spectra
were recorded at 298 K. Proton decoupling was applied for 13C and
31P spectra. HRMS was recorded with a Water Q-TOF Premier
MS. X-ray crystallographic analyses were performed with a Bruker
X8 APEX CCD diffractometer or a Bruker Kappa CCD dif-
Phosphirane 6 appears to be an efficient precursor of
ferrocenylphosphinidene complex 7 working between 80
and 100 °C with a very easily eliminated byproduct (cyclo-
hexene). In view of the numerous applications of ferrocenyl- fractometer.
phosphines as ligands for transition metals in homogeneous
Ring Opening of 3 by HCl: Phosphirane 3 (33 mg, 0.07 mmol) was
catalysis,[13] it is quite interesting to have a new powerful
tool[14] to synthesize additional members of this family of
ligands. Given that the ferrocenyl substituent is known to
stabilize electron-deficient centers, it was interesting to have
a look at the structure of 7. The computed geometrical
structure of 7 is shown in Figure 5. It is immediately clear
that there is an attractive interaction between P and Fe.
This interaction leads to displacement of phosphorus from
the cyclopentadienyl plane toward the iron atom. The out-
stirred with aluminum trichloride contaminated with HCl (28 mg,
0.21 mmol) in CH2Cl2 (2 mL) for 45 min at room temperature.
Adding a drop of wet toluene into the mixture favored the reaction.
The crude product was purified by chromatography (hexane) on a
jacketed column at –10 °C to prevent partial hydrolysis of 4,which
1
afforded pure complex 4 (12 mg, 33.7%). H NMR (CDCl3): δ =
3
1.28 (m, 1 H, CH2), 1.42 (m, 4 H, CH2), 1.79 (d, JHP = 12 Hz, 1
H, CH2), 2.02 (s, 2 H, CH2), 2.30 (m, 2 H, CH2), 2.42 (m, 1 H,
2
CHP) ppm. 13C NMR (CDCl3): δ = 25.75 (s, CH2), 26.18 (d, JCP
3
1
= 15 Hz, CH2), 26.97 (d, JCP = 2.5 Hz, CH2), 57.19 (d, JCP
=
=
=
2
2
5 Hz, CHP), 195.08 (d, JCP = 7.5 Hz, cis-CO), 198.01 (d, JCP
42.8 Hz, trans-CO) ppm. 31P NMR (CDCl3): δ = 162.9 (1JPW
320.8 Hz) ppm. MS: m/z = 507.9223 (calcd. for C11H11O5Cl2PW
m/z = 507.9230).
1-(2-Thienyl)phosphirane Complex 5: A mixture of phosphirane 3
(90 mg, 0.19 mmol), aluminum trichloride (151 mg, 1.14 mmol),
and thiophene (0.09 mL, 1.14 mmol) was stirred in CH2Cl2 (3 mL)
for 1 h at room temperature. Purification by cold column
chromatography (–10 °C, hexane) yielded phosphirane 5 (26 mg,
26.3%). 1H NMR (CD2Cl2): δ = 1.47 (m, 4 H, CH2), 1.90 (m, 2
H, CH2), 2.28 (m, 2 H, CHP), 2.31 (m, 2 H, CH2), 7.08 (m, 1 H,
C4H3S), 7.30 (m, 1 H, C4H3S), 7.48 (m, 1 H, C4H3S) ppm. 13C
NMR (CD2Cl2): δ = 21.06 (d, JCP = 4 Hz, CH2), 22.06 (d, JCP
=
3 Hz, CH2), 26.05 (d, 1JCP = 14 Hz, CHP), 127.70 (d, JCP = 11 Hz,
C4H3S), 129.76 (d, JCP = 2 Hz, C4H3S), 133.98 (d, JCP = 2 Hz,
1
2
C4H3S), 139.20 (d, JCP = 24 Hz, C4H3S), 195.66 (d, JCP = 8 Hz,
cis-CO), 197.18 (d, JCP = 31.2 Hz, trans-CO) ppm. 31P NMR
2
Figure 5. Computed structure of ferrocenylphosphinidene complex
7. Main distances [Å] and angles [°]: P21–C16 1.781, P21–W22
2.481. P21–Fe11 3.198; C16–P21–W22 115.51.
(CD2Cl2): δ = –171.5 (1JPW = 269 Hz) ppm. HRMS: calcd. for
C15H13O5PSW 519.9731; found 519.9709.
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SHORT COMMUNICATION
1-Ferrocenylphosphirane Complex 6: A mixture of phosphirane 3
(33 mg, 0.07 mmol), aluminum trichloride (55 mg, 0.42 mmol), and
ferrocene (78 mg, 0.42 mmol) was stirred in CH2Cl2 (2 mL) for 1 h
at room temperature to give phosphirane 6. Purification by cold
column chromatography (–10 °C; hexane/dichloromethane, 9:1)
yielded 6 (20 mg, 46%). 1H NMR (CDCl3): δ = 1.48 (m, 4 H, CH2),
1.86 (m, 2 H, CH2), 2.05 (m, 2 H, CHP), 2.26 (m, 2 H, CH2), 4.18
(d, JHH = 2 Hz, 2 H, C5H4P), 4.23 (s, 5 H, C5H5), 4.33 (s, 2 H,
CCDC-1014059 (for 5) and -1014060 (for 8) contain the supple-
mentary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Supporting Information (see footnote on the first page of this arti-
cle): X-ray crystal structure analyses of 5 and 8 and NMR spectra
of compounds 4–6 and 8–10.
2
C5H4P) ppm. 13C NMR (CDCl3): δ = 21.57 (d, JCP = 3.8 Hz,
3
1
CH2), 22.66 (d, JCP = 2.7 Hz, CH2), 26.67 (d, JCP = 12.3 Hz,
Acknowledgments
3
CHP), 69.65 (s, C5H5), 70.72 (d, JCP = 7.5 Hz, C5H4P), 71.92 (d,
2JCP = 13.4 Hz, C5H4P), 79.60 (d, JCP = 30.4 Hz, C5H4P), 196.34
1
The authors thank the Nanyang Technological University in Singa-
pore for financial support of this work.
2
2
(d, JCP = 8 Hz, cis-CO), 197.05 (d, JCP = 29.2 Hz, trans-CO)
ppm. 31P NMR (CDCl3): δ = –166.6 (1JPW = 264 Hz) ppm. HRMS:
calcd. for C21H19O5PWFe 621.9829; found 621.9814.
[1] G. Märkl, W. Hölzl, I. Trötsch-Schaller, Tetrahedron Lett. 1987,
28, 2693.
[2] E. Niecke, M. Leuer, M. Nieger, Chem. Ber. 1989, 122, 453.
[3] W. Schnurr, M. Regitz, Z. Naturforsch. B 1988, 43, 1285.
[4] B. Deschamps, L. Ricard, F. Mathey, Polyhedron 1989, 8, 2671.
[5] P. Le Floch, F. Mathey, Synlett 1991, 743.
1-Ferrocenylphosphirane Complex 8: Phosphirane
6 (40 mg,
0.06 mmol) was stirred with trans-stilbene (65 mg, 0.36 mmol) in
toluene (2 mL) at 100 °C for 7.5 h. Purification by cold column
chromatography (–10 °C; hexane/dichloromethane, 8:2) gave phos-
phirane 8 (15 mg, 34.9%). 1H NMR (CD2Cl2): δ = 3.70 (s, 2 H,
CHP), 3.70 (s, 1 H, C10H9Fe), 4.22–4.31 (m, 8 H, C10H9Fe), 7.23–
7.47 (m, 10 H, aromatic CH) ppm. 13C NMR (CD2Cl2): δ = 35.40
[6] N. H. T. Huy, T. V. Gryaznova, L. Ricard, F. Mathey, Organo-
metallics 2005, 24, 2930.
1
1
[7] M. P. Duffy, F. Mathey, J. Am. Chem. Soc. 2009, 131, 7534.
[8] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B.
Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li,
H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Son-
nenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hase-
gawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai,
T. Vreven, J. A. Montgomery Jr., J. E. Peralta, F. Ogliaro, M.
Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Starov-
erov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari,
A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N.
Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V.
Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Strat-
mann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W.
Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski,
G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D.
Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski,
D. J. Fox, Gaussian 09, revision D.01, Gaussian, Inc., Wall-
ingford, CT, 2013.
(d, JCP = 9.7 Hz, CHP), 39.81 (d, JCP = 14.6 Hz, CHP), 70.29 (s,
C5H5), 71.52 (s, C5H4), 71.85 (s, C5H4), 71.95 (s, C5H4), 76.38 (s,
C5H4), 76.61 (s, C5H4), 127.66 (s, aromatic CH), 128.0 (s, aromatic
CH), 129.19 (s, aromatic CH), 129.26 (s, aromatic CH), 129.32 (s,
aromatic CH), 129.62 (s, aromatic CH), 130.49 (s, aromatic CH),
2
135.91 (s, ipso-C), 137.56 (s, ipso-C), 196.36 (d, JCP = 8.0 Hz, cis-
2
CO), 197.81 (d, JCP = 32.3 Hz, trans-CO) ppm. 31P NMR
(CD2Cl2): δ = –130.9 (1JPW = 268.9 Hz) ppm. HRMS: calcd. for
C29H21O5PWFe 719.9986; found: 720.0004.
1-Ferrocenylphosphirene Complex 9: Phosphirane
6 (17 mg,
0.03 mmol) was stirred with diphenylacetylene (32 mg, 0.18 mmol)
in toluene (1.5 mL) at 100 °C for 7.5 h. Purification by cold column
chromatography (–10 °C; hexane/dichloromethane, 8:2) yielded
1
phosphirene 9 (10 mg, 46.7%). H NMR (CD2Cl2): δ = 4.16 (s, 5
H, C5H5), 4.21 (m, 2 H, C5H4P), 4.36 (m, 2 H, C5H4P), 7.50–7.93
(m, 10 H, aromatic CH) ppm. 13C NMR (CD2Cl2): δ = 70.13 (s,
C5H5), 71.83 (d, JCP = 7.3 Hz, C5H4P), 72.74 (d, JCP = 14.8 Hz,
[9] B. Deschamps, L. Ricard, F. Mathey, Polyhedron 1989, 8, 2671.
[10] M. Cherkaoui, A. Boutalib, Orbital: Electron. J. Chem. 2012,
4, 235.
[11] A. Marinetti, F. Mathey, J. Fischer, A. Mitschler, J. Chem. Soc.,
Chem. Commun. 1982, 667.
2
C5H4P), 80.85 (d, JCP = 7.8 Hz, C5H4P), 128.30 (d, JCP = 6.2 Hz,
1
ipso-Ph), 129.32 (d, JCP = 7.8 Hz, CP), 129.81 (s, aromatic CH),
130.56 (d, JCP = 4.8 Hz, aromatic CH), 130.98 (s, aromatic CH),
196.97 (d, JCP = 8.6 Hz, cis-CO), 198.64 (d, JCP = 32.6 Hz, trans-
CO) ppm. 31P NMR (CD2Cl2): δ = –161.5 (1JPW = 272.2 Hz) ppm.
HRMS: calcd. for C29H19O5PWFe 717.9858; found 717.9829.
[12] A. Jayaraman, B. T. Sterenberg, Organometallics 2013, 32, 745.
[13] A. Fihri, P. Meunier, J.-C. Hierso, Coord. Chem. Rev. 2007, 251,
2017; R. C. J. Atkinson, V. C. Gibson, N. J. Long, Chem. Soc.
Rev. 2004, 33, 313; T. Hayashi, M. Kumada, Acc. Chem. Res.
1982, 15, 395.
[14] Recent reviews on the chemistry of electrophilic terminal phos-
phinidene complexes: J. C. Slootweg, K. Lammertsma, Sci.
Synth. 2009, 42, 15; R. Waterman, Dalton Trans. 2009, 18; M.
Rani, Synlett 2008, 2078; F. Mathey, Dalton Trans. 2007, 1861;
K. Lammertsma, Top. Curr. Chem. 2003, 229, 95; K. Lam-
mertsma, M. J. M. Vlaar, Eur. J. Org. Chem. 2002, 1127; F. Ma-
they, N. H. Tran Huy, A. Marinetti, Helv. Chim. Acta 2001, 84,
2938.
Ferrocenylhydroxyphosphine Complex 10: Phosphirane 6 (12 mg,
0.019 mmol) was stirred with a drop of deionized water in toluene
(1.5 mL) at 100 °C for 7.5 h. Purification by cold column
1
chromatography (–10 °C, ethyl acetate) gave 10 (4 mg, 37.7%). H
NMR (CDCl3): δ = 4.30 (s, 5 H, C5H5), 4.50 (m, 2 H, C5H4P),
4.55 (s, 1 H, C5H4P), 4.58 (s, 1 H, C5H4P), 8.01 (d, 1JHP = 365.2 Hz,
1 H, HP) ppm. 13C NMR (CDCl3): δ = 69.60 (s, C5H5), 72.11 (d,
JCP = 9.4 Hz, C5H4P), 72.57 (d, JCP = 8.6 Hz, C5H4P), 72.89 (d,
2
JCP = 6.9 Hz, C5H4P), 73.33 (d, JCP = 20.1 Hz, C5H4P), 78.85 (d,
2
1JCP = 50.2 Hz, C5H4P), 196.14 (d, JCP = 7.9 Hz, cis-CO), 198.84
[15] V. Nesterov, A. Espinosa, G. Schnakenburg, R. Streubel, Chem.
Eur. J. 2014, 20, 7010.
2
(d, JCP = 23.7 Hz, trans-CO) ppm. 31P NMR (CH2Cl2): δ = 71.0
1
(1JPW = 268.7 Hz, JPH = 364.9 Hz) ppm. HRMS: calcd. for
Received: July 15, 2014
C15H11O6PWFe 557.9152; found 557.9137.
Published Online: September 8, 2014
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© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim