Synthesis of novel O,P,C-cage complexes via thermal C-O ring opening of an oxaphosphirane W(CO)5 complex

Article abstract of DOI:10.1021/om7012953

A facile and highly stereoselective synthesis of novel O,P,C-cage complexes via thermal C-O ring opening of an oxaphosphirane W(CO)₅ complex is described. All compounds were unambiguously characterized by elemental analysis, multinuclear NMR, IR, MS, and single-crystal X-ray diffraction studies.

Full text of DOI:10.1021/om7012953

2664
Organometallics 2008, 27, 2664–2667
Notes
Synthesis of Novel O,P,C-Cage Complexes via Thermal C-O Ring
Opening of an Oxaphosphirane W(CO)5 Complex
Maren Bode,† Gregor Schnakenburg,† Peter G. Jones,‡ and Rainer Streubel*,†
Institut fu¨r Anorganische Chemie, Rheinische Friedrich-Wilhelms-UniVersita¨t Bonn,
Gerhard-Domagk-Strasse 1, 53121 Bonn, Germany, and Institut fu¨r Anorganische and Analytische Chemie,
Technische UniVersita¨t Braunschweig, Hagenring 30, 38106 Braunschweig, Germany
ReceiVed December 29, 2007
Chart 1. Epoxides I and Related Three-Membered Ring
Systems II-IV (R denotes ubiquitous organic substituents; E
denotes a lone pair, R2, O, NR, or a W(CO)5 group)
Summary: A facile and highly stereoselectiVe synthesis of noVel
O,P,C-cage complexes Via thermal C-O ring opening of an
oxaphosphirane W(CO)5 complex is described. All compounds
were unambiguously characterized by elemental analysis, multi-
nuclear NMR, IR, MS, and single-crystal X-ray diffraction
studies.
Introduction
and hexafluoroacetone.7 Oxaphosphirane transition-metal com-
plexes IV (E ) W(CO)5), first described in 1990 by Mathey
and co-workers, were prepared by epoxidation of phosphaalkene
complexes with meta-chloroperbenzoic acid.8
Epoxides I (oxiranes) (Chart 1) are important building blocks
in organic synthesis and polymer chemistry.1,2 In contrast,
oxaziridines II, in which one of the CR2 moieties is (formally)
exchanged for an NR group, have received much less attention,
which is also true for the silicon (III) and phosphorus analogues
(IV) (Chart 1). The latter have been (mostly) claimed as reactive
intermediates,3 and up to now only one stable derivative of III4
has been described; IV (E ) lone pair) is still unknown.
Theoretical calculations were recently performed on derivatives
of IV (E ) lone pair)5 and IV (E ) two R groups).6 In 1978,
σ4λ5-oxaphosphiranes IV (E ) NR) were synthesized via a
[2+1] cycloaddition reaction of an iminophosphine derivative
Later, thermal ring cleavage of a 2H-azaphosphirene W(CO)5
complex in the presence of an aldehyde9 or a ketone10 enabled
access to derivatives having P-alkyl substituents. Recent at-
tempts to exploit this route using a P-C5Me5-substituted 2H-
azaphosphirene complex and benzaldehyde failed, and a 1,3,4-
dioxaphospholane complex with a symmetrical substitution
pattern at the carbon centers was obtained instead.11 Very
recently, we gained novel access to P-bis(trimethylsilyl)methyl
oxaphosphirane tungsten complexes using a transient Li/Cl
phosphinidenoid tungsten complex, which reacted in situ with
benz- or isobutyraldehyde.12 To the best of our knowledge
neither P- nor C-functional oxaphosphirane complexes are
known so far. Here, the synthesis and structural characterization
of the first P-functional oxaphosphirane complex and its
selective transformation into novel O,P,C-cage complexes are
described.
* Corresponding author. Fax: (49)228-739616. Tel: (49)228-735345.
E-mail: r.streubel@uni-bonn.de.
† Rheinische Friedrich-Wilhelms-Universita¨t Bonn.
‡ Technische Universita¨t Braunschweig.
(1) (a) Nugent, W. A.; RajanBabu, T. V. J. Am. Chem. Soc. 1988, 110,
8561. (b) Jacobsen, E. N.; Wu, M. H. In ComprehensiVe Asymmetric
Catalysis I-III; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer-
Verlag: Berlin, 1999; Vol. 3, p 1309. (c) Gansa¨uer, A.; Bluhm, H. Chem.
ReV. 2000, 100, 2771.
(2) Review: Coates, G. W.; Moore, D. R. Angew. Chem. 2004, 116,
6784. ; Angew. Chem., Int. Ed. 2004, 43, 6618.
(3) (a) Ando, W.; Ikeno, M.; Sekiguchi, A. J. Am. Chem. Soc. 1977,
99, 6447. (b) Jutzi, P.; Eikenberg, D.; Bunte, E.-A.; Moehrke, A.; Neumann,
B.; Stammler, H.-G. Organometallics 1996, 15, 1930. (c) Wang, Y.; Dolg,
M. Tetrahedron 1999, 55, 12751. (d) Khabashesku, V. N.; Kudin, K. N.;
Margrave, J. L.; Fredin, L. J. Organomet. Chem. 2000, 595–248.
(4) Ando, W.; Hamada, Y.; Sekiguchi, A. Tetrahedron Lett. 1982, 23,
5323.
(7) (a) Ro¨schenthaler, G. V.; Sauerbrey, K.; Schmutzler, R. Chem. Ber.
1978, 111, 3105. (b) Seifert, F. U.; Ro¨schenthaler, G. V. Z. Naturforsch. B
1993, 48, 1089.
(8) Bauer, S.; Marinetti, A.; Ricard, L.; Mathey, F. Angew. Chem. 1990,
102, 1188. ; Angew. Chem., Int. Ed. Engl. 1990, 29, 1166.
(9) Streubel, R.; Kusenberg, A.; Jeske, J.; Jones, P. G. Angew. Chem.
1994, 106, 2564. ; Angew. Chem., Int. Ed. Engl. 1994, 33, 2427.
(10) Streubel, R.; Ostrowski, A.; Wilkens, H.; Ruthe, F.; Jeske, J.; Jones,
P. G. Angew. Chem. 1997, 109, 409. Angew. Chem., Int. Ed. Engl. 1997,
36, 378.
(5) For calculations concerning type IV derivatives, see (a): Schoeller,
W. W. In Multiple Bonds and Low Coordination in Phosphorus Chemistry;
Regitz, M., Scherer, O. J., Eds.; Georg Thieme Verlag: Stuttgart, 1990; p
1. (b) Goumanns, T. P. M.; Ehlers, A. W.; Lammertsma, K.; Wu¨rthwein,
E. U. Eur. J. Org. Chem. 2003, 2941.
(6) (a) For calculations concerning type V derivatives, see: Ikeda, H.;
Inagaki, S. J. Phys. Chem. A 2001, 10711. (b) Chesnut, D. B.; Quin, L. D.
Tetrahedron 2005, 61, 12343. (c) Savostina, L. I.; Aminova, R. M.; Mironov,
V. F. Russ. J. Gen. Chem. 2006, 76, 1031.
(11) Bode, M.; Nieger, M.; Streubel, R. Organometallics 2007, 26, 245.
(12) Ozbolat, A.; von Frantzius, G.; Marinas Pe´rez, J.; Nieger, M.;
Streubel, R. Angew. Chem. 2007, 119, 9488. Angew. Chem., Int. Ed. 2007,
46, 9327.
10.1021/om7012953 CCC: $40.75
2008 American Chemical Society
Publication on Web 04/24/2008

Notes
Organometallics, Vol. 27, No. 11, 2008 2665
Scheme 1. Synthesis of Oxaphosphirane Complex 3 Using Dichloro(organo)phosphane Complex 1 and Benzaldehyde (2a), and
Thermal Ring-Opening Reactions of 3
Scheme 2. Oxaphosphirane Complex 3 (A) and Isomeric Forms (B-D)
acyclic diradical complex D (Scheme 2), which rapidly react
with the P-C5Me5 group.15,16
Results and Discussion
The reaction of dichloro(organo)phosphane complex 113 with
tert-butyllithium in diethyl ether at low temperature in the
presence of 12-crown-4 and benzaldehyde (2a) afforded selec-
tively the oxaphosphirane complex 3 (Scheme 1). We assume
that an intermediate Li/Cl exchange reaction occurred in 1, thus
leading to a transient Li/Cl phosphinidenoid complex.12 As we
wished to gain access to asymmetrically substituted 1,3,4-
dioxaphospholane complexes 4, we studied the thermal reaction
of complex 3 with aldehydes 2a,b in toluene. To our surprise,
we did not obtain the expected heterocycle complexes 4. Instead,
complexes 5 and 6 were obtained regioselectively, which have
novel, different O,P,C-cage ligands, showing that an oxaphos-
phirane C-O ring opening had occurred (Scheme 1). It is also
remarkable that the former P-C5Me5 group was transformed into
a partially saturated ring that is incorporated into different
polycyclic structures: Noteworthy is that a P-C bond cleavage
must have occurred at one point.
Although we do not have direct evidence for primarily formed
intermediates, the observation that complex 4 was not detected
is important, and therefore we conclude that no valence
isomerization (A f B) of 3 (A) to the intermediate phosphac-
arbonyl-ylide complex B had occurred. Further support stems
from the observation that the related P-bis(trimethylsilyl)methyl
derivative of complex 39 does not react with aldehydes 2a,b
under the same conditions.14 Therefore, a cleavage of the C-O
bond in 3 (A) seems to occur, generating either the η2-
coordinated alkylidene(oxo)phosphorane complex C or the
Both could be starting points for multistep reactions leading
finally to complexes 5 and 6. The following arguments disfavor
other conceivable primary steps: (1) homolytic P-CCp* bond
cleavage reactions of related three-membered P-heterocyclic
ligands having P-C5Me5 substituents such as phosphiranes and
1H-phosphirenes are unknown, and (2) intermolecular [4 + 2]
cycloaddition reactions of such P-bonded C5Me5 groups have
not been observed before.17 Recently, an interesting ring
enlargement of a P-bonded C5Me5 group (of a dinuclear µ2-
phosphinidene complex) has been observed to occur during
reaction with a phosphaalkyne derivative, leading finally to a
1,2-diphospha-cyclooctatetraene complex.18
The molecular structures of complexes 3, 5, and 6 were
unambiguously established by elemental analysis, NMR and IR
spectroscopy, and single-crystal X-ray diffraction studies (Figure
(15) Alkylidene(oxo)phosphoranes are known to undergo various cy-
cloaddition reactions, in principle, but only at the PdC double bond system.
For examples, see: Heydt, H. In Multiple Bonds and Low Coordination in
Phosphorus Chemistry; Regitz, M., Scherer, O. J., Eds.; Georg Thieme
Verlag: Stuttgart, 1990; p 381. As alkylidene(oxo)phosphorane complexes
are unknown as such, nothing is known about an isomerization of 7 to the
diradical complex 8.
(16) In principle, complex 8 could be formed directly via homolytic
C-O bond cleavage from 3; we are currently trying to calculate the different
barriers for the P-C, P-O, and C-O cleavage reactions in oxaphosphirane
complexes. For the problem of C-C vs C-O bond cleavage in oxiranes,
see: Tian, F.; Baker, J. M.; Smart, B. E. J. F. Chem. 2002, 114, 107–111.
(17) (a) Streubel, R.; Bode, M.; Schiemann, U.; Wismach, C.; Jones,
P. G.; Monsees, A. Z. Allg. Anorg. Chem. 2004, 630, 1215. (b) Bode, M.;
Universita¨t Bonn,planned Ph.D. thesis.
(13) 1b was synthesized according to: Jutzi, P.; Saleske, H.; Nadler, D.
J. Organomet. Chem. 1976, 118, C8.
(18) Scheer, M.; Himmel, D.; Johnson, B. P.; Kuntz, C.; Schiffer, M.
Angew. Chem. 2007, 119, 4045–4049. Angew. Chem., Int. Ed. 2007, 46,
3971-3975.
(14) Marinas Pe´rez, J. Universita¨t Bonn, planned Ph.D. thesis.

2666 Organometallics, Vol. 27, No. 11, 2008
Notes
5 and 6 are very similar to each other (δ ) 152.7 ppm, 1J(W,P)
1
) 334.4 Hz (5) and δ ) 155.1 ppm, J(W,P) ) 334.4 Hz (6))
but different from the expected 1,3,4-dioxaphospholanes, which
show values at approximately 138 ppm and phosphorus-tungsten
coupling constants of 280-285 Hz. The structural differences
ofthecagesof5and6arerevealedthroughthephosphorus-hydrogen
couplings with the C(Ph)H proton: whereas the 31P and 1H NMR
spectra of 6 clearly showed a coupling constant of 12.8 Hz, a
much smaller coupling constant of 4.5 Hz was determined (only)
1
from the H NMR spectrum of 5.
The solid state structures of 5 and 6, shown in Figures 1 and
2, unambiguously confirm the constitutions. The main differ-
ences between 5 and 6 are found within the particular cage
moieties but shall not be discussed further; the geometries at
phosphorus are quite similar and the P-O is ca. 1.61 Å and
P-C bond distances are ca. 1.83 Å; such values are also found
for polycyclic phosphite and O,P,C-cage compounds.19 The
bond angle sums ∑ °P of the PR3 units are 305.5° (5) and 301.3°
(6), respectively.
Figure 1. Structure of complex 3 (50% probability level; hydrogen
atoms except H1 are omitted for clarity). Selected bond lengths
[Å] and angles [deg]: W-P 2.4694(7), P-O(1) 1.667(2), P-C(1)
1.805(3), P-C(8) 1.855(3), O(1)-C(1) 1.468(3), O(1)-P-C(1)
49.84(11), C(1)-O(1)-P 69.97(15), O(1)-C(1)-P 60.20(14).
Conclusions
Herein, we describe facile synthesis of the first P-functional
oxaphosphirane complex and its use in thermal reactions that
lead to the regioselective formation of novel O,P,C-cage ligands.
It illustrates nicely the versatility of P-bonded C5Me5 groups
in P,C-cage synthesis20 and broadens the applicability using
aldehydes as new cooperative building blocks. Current studies
are devoted to elucidate the mechanism, especially with regard
to the discussed reactive intermediates, and to explore the
chemistry of the uncoordinated O,P,C-cage ligands.
Figure 2. Structure of complex 5 (50% probability level; hydrogen
atoms except H6 and H7 are omitted for clarity). Selected bond
lengths [Å] and angles [deg]: W-P 2.453(6), P-O(6) 1.606(17),
P-O(7)1.601(14),P-C(7)1.845(2),O(6)-C(6)1.475(3),O(7)-C(10)
1.501(3), C(6)-C(8) 1.529(3), C(7)-C(9) 1.584(3); O(6)-P-O(7)
101.92(8),O(6)-P-C(7)99.16(9),O(7)-P-C(7)104.38(9),C(6)-O(6)-P
115.66(14), C(10)-O(7)-P 116.71(12), C(9)-C(7)-P 109.75(13),
O(6)-C(6)-C(8) 112.49(19).
Experimental Section
All operations were performed in an atmosphere of purified and
dried argon. Solvents were distilled from sodium. NMR data were
recorded on a Bruker Avance 300 spectrometer at 30 °C using C6D6
(3) or CDCl3 (5, 6) as solvent and internal standard; shifts are given
relative to tetramethylsilane (13C: 75.5 MHz) and 85% H3PO4 (31P:
121.5 MHz). Mass spectra were recorded on a Kratos MS 50
spectrometer (EI, 70 eV); only m/z values are given. Elemental
analyses were performed using an Elementa (Vario EL) analytical
gas chromatograph. Infrared spectra were collected on FT-IR
Nicolet 380. Melting points were obtained on a Bu¨chi 535 capillary
apparatus. X-ray crystallographic analysis of 3, 5, and 6: Data were
collected on a Nonious KappaCCD diffractometer at 123 K using
Mo KR radiation (λ ) 0.71073 Å) (3, 5) and a Bruker SMART
diffractometer at 133 K (6). The structures were refined by full-
matrix least-squares on F2 (SHELXL-9721). All non-hydrogens were
refined anisotropically. The hydrogen atoms were included in
calculated positions using a riding model.
Synthesis of Complex 3. To a solution of 230 mg (0.41 mmol)
of 1 in 5 mL of diethyl ether were added 74 µL (0.46 mmol) of
12-crown-4 and then 46 µL (0.46 mmol) of benzaldehyde. The
solution was cooled to -80 °C, and a solution, prepared from 0.3
mL (0.46 mmol) of tert-butyllithium (1.5 mol/L in pentane) and 5
mL of diethyl ether at -80 °C, was added dropwise. The solutions
were then stirred for 90 min while gently warming to -20 °C. The
Figure 3. Structure of complex 6 (50% probability level; hydrogen
atoms except H6 and H7 are omitted for clarity). Selected bond
lengths [Å] and angles [deg]: W-P 2.457(4), P-O(6) 1.614(11),
P-O(7) 1.609(10), P-C(7) 1.829(14), O(6)-C(6) 1.451(15),
O(7)-C(10) 1.488(17), C(6)-C(8) 1.579(19), C(7)-C(9) 1.564(19),
O(6)-P-O(7) 106.80(6), O(6)-P-C(7) 100.24(6), O(7)-P-C(7)
94.29(6), C(6)-O(6)-P 124.51(9), C(10)-O(7)-P 112.58(8),
C(9)-C(7)-P 98.43(9), O(6)-C(6)-C(8) 112.16(10).
(19) (a) Aroney, M. J.; Davies, M. S.; Hambley, T. W.; Pierens, R. K.
J. Chem. Soc., Dalton Trans. 1994, 91. (b) Nimrod, D. M.; Fitzwater, D. R.;
Verkade, J. G. J. Am. Chem. Soc. 1968, 90, 2780. (c) Wroblewski, A. E.;
Verkade, J. G. J. Am. Chem. Soc. 1996, 118, 10168. (d) Wei, L.; LaCour,
T. G.; Fuchs, P. L. J. Am. Chem. Soc. 2002, 124, 4548.
1, 2, and 3). The NMR data of oxaphosphirane complex 3 are
closely related to those of the P-bis(trimethylsilyl)methyl
derivative9 reported recently, although the 31P resonance of 3
1
(δ ) 31.6 ppm; J(W,P) ) 309.0 Hz) is upfield shifted by a
(20) Presley, O. C.; Green, M.; Jeffery, J. C.; Leiner, E.; Murray, M.;
Russell, C. A.; Scheer, M.; Vogel, U. J. Chem. Soc., Chem. Commun. 2006,
4542–4544.
∆δ value of 10 ppm, and also the oxaphosphirane ring carbon
resonance is found at 55.5 ppm (J(P,C) ) 17.5 Hz), which is
in the upfield region. The 31P{1H} NMR data of the polycycles
(21) Sheldrick, G. M. SHELXL-97; Universita¨t Go¨ttingen, 1997.

Notes
Organometallics, Vol. 27, No. 11, 2008 2667
solvents were then removed in Vacuo (ca. 0.01 bar), and the residue
was extracted with 20 mL of n-pentane. The product was purified
by column chromatography (Al2O3, -10 °C) using (1) petroleum
ether and (2) a mixture of petroleum ether with diethyl ether (95:
5). After evaporation the crude product was washed with n-pentane
at -70 °C.
J(P,C) ) 10.7 Hz, Ph), 133.0 (s, Ccage), 129.3 (d, J(P,C) ) 9.4 Hz,
Ph), 141.5 (s, Ccage), 194.5 (dSat, J(W,C) ) 125.8 Hz, J(P,C) )
9.7 Hz, cis-CO), 198.5 (d, J(P,C) ) 32.7 Hz, trans-CO). 31P NMR:
δ 152.7 (br, sSat,
1J(W,P) ) 334.4 Hz). MS: m/z (%): 640 (62)
[(M)+]. IR (KBr; ν(CO)): ν˜ 1924 (s), 1955 (s), 1991 (m), 2075
(m) [cm-1]. Anal. Calcd: C 45.02 H 3.94. Exptl: C 44.96 H 3.96.
X-ray crystallographic analysis: Suitable colorless single crystals
were obtained from concentrated n-pentane/diethyl ether solutions
upon slow cooling to 4 °C. C24H25O7PW; crystal size 0.40 × 0.40
× 0.30 mm3, monoclinic, P21/n, a ) 10.4536(2) Å, b ) 15.8144(4)
Å, c ) 14.8700(4) Å, ꢀ ) 99.6078(15)°, V ) 2423.79(10) Å3, Z
) 4, 2θmax ) 60°, collected (independent) reflections ) 26 294
(7065), Rint ) 0.0479, µ ) 4.873 mm˜1, 304 refined parameters, R1
(for I > 2σ(I)) ) 0.0224, wR21 (for all data) ) 0.0438, max./min.
residual electron density ) 1.699/-1.139 e Ř3.
3: pale yellow solid; yield 54 mg (0.09 mmol, 22%); mp 103 °C
(dec). 1H NMR: δ 0.83 (d, 3H, 3J(P,H) ) 11.3 Hz, Cp*(C1)-CH3),
1.65 (m, 6H, Cp*-CH3), 1.68 (s, 3H, Cp*-CH3), 1.93 (s, 3H, Cp*-
CH3), 4.23 (s, 1H, POCH), 7.05-7.37 (m, 5H, Ph). 13C{1H} NMR:
δ 9.5 (d, J(P,C) ) 3.2 Hz, Cp*-CH3), 10.1 (d, J(P,C) ) 2.3 Hz,
Cp*-CH3), 10.2 (d, J(P,C) ) 1.3 Hz, Cp*-CH3), 10.6 (d, J(P,C) )
1.6 Hz, Cp*-CH3), 12.0 (d, J(P,C) ) 4.8 Hz, Cp*(C1-CH3), 55.5
(d, J(P,C) ) 17.5 Hz, PCO), 63.0 (d, 1J(P,C) ) 10.0 Hz, Cp*(C1)),
125.0 (d, J(P,C) ) 2.9 Hz, Ph), 127.2 (d, J(P,C) ) 2.3 Hz, Ph),
127.5 (d, J(P,C) ) 2.3 Hz, Ph), 131.6 (d, J(P,C) ) 7.4 Hz, Cp*),
134.0 (s, Ph), 136.8 (d, J(P,C) ) 1.6 Hz, Cp*), 140.7 (d, J(P,C) )
6: colorless solid; yield 50 mg (0.071 mmol, 20%); mp 170-171
1
°C. Selected NMR data: H NMR: δ 0.66 (s, 3H, CH3), 0.91 (s,
2
6.1 Hz, Cp*), 143.0 (d, J(P,C) ) 7.8 Hz, Cp*), 194.8 (d, J(P,C)
3H, CH3), 1.33 (s, 3H, CH3), 1.76 (s, 3H, CH3), 1.77 (s, 3H, CH3),
4.08 (s, 1H, C(H)Ph), 5.12 (d, J(P,H) ) 12.8 Hz, 1H, C(H)Ph),
7.20-7.38 (mc, 10H, Ph). 13C{1H} NMR: δ 10.1 (s, Ccage-CH3),
10.6 (s, Ccage-CH3), 18.6 (d, J(P,C) ) 5.4 Hz, Ccage-CH3), 19.0 (s,
Ccage-CH3), 21.1 (d, J(P,C) ) 4.2 Hz, Ccage-CH3), 55.8 (s, Ccage),
56.1 (d, J(P,C) ) 22.1 Hz, Ccage-Ph), 60.1 (d, J(P,C) ) 3.6 Hz,
Ccage), 87.6 (d, J(P,C) ) 13.1 Hz, Ccage-Ph), 104.0 (d, J(P,C) )
9.5 Hz, Ccage), 127.5 (s, Ph), 127.8 (s, Ph), 128.5 (s, Ph), 128.9 (s,
Ph), 134.9 (d, J(P,C) ) 5.4 Hz, Ccage), 135.4 (s, Ccage), 138.4 (s,
Ccage), 138.6 (d, J(P,C) ) 1.2 Hz, Ccage), 195.5 (dSat, J(W,C) )
125.8 Hz, J(P,C) ) 9.5 Hz, cis-CO), 198.6 (d, J(P,C) ) 33.4 Hz,
trans-CO). 31P NMR: δ 155.1 (dSat, J(W,P) ) 334.4 Hz, J(P,H)
)12.7 Hz); MS: m/z (%): 702 (100) [(M)+]. IR (KBr; ν(CO)): ν˜
1929 (s), 1935 (s), 1983 (m), 2074 (m) [cm-1]. Anal. Calcd: C
49.59 H 3.87. Exptl: C 49.58 H 3.99. X-ray crystallographic
analysis: Suitable colorless single crystals were obtained from
concentrated diethyl ether solutions. C29H27O7PW, crystal size 0.27
× 0.21 × 0.15 mm, triclinic, space group P(-1), a ) 8.8233(8)
Å, b ) 10.7260(10) Å, c ) 15.0798(14) Å, R ) 92.218(4)°, ꢀ )
105.029(4)°, γ ) 93.583(4)°, U ) 1373.4(2) Å3, Z ) 2, 2θmax 61°,
collected (independent) reflections 29 773 (8358), Rint ) 0.022, µ
) 4.31 mm-1, 348 refined parameters, R1 (for I > 2σ(I)) ) 0.0152,
wR21 (for all data) ) 0.0375, max./min. residual electron density
) 1.14/-0.36 e Ř3.
) 8.4 Hz, J(W,C) ) 125.2 Hz, cis-CO), 197.3 (d, 2J(P,C) ) 37.5
1
Hz, trans-CO). 31P{1H} NMR: δ ) 31.6 (sSat, J(W,P) ) 309.0
Hz). MS: m/z (%): 596 (17) [(M)+]. IR (KBr; ν(CO)): ν˜ 1937 (m),
1992 (s), 2074 (s) [cm-1]. Aanl. Calcd: C 44.32 H 3.55. Exptl: C
44.39 H 3.69. X-ray crystallographic analysis: Suitable pale yellow
single crystals were obtained from concentrated n-pentane solutions
upon slow cooling to 4 °C. C22H21O6PW; crystal size 0.60 × 0.40
× 0.40 mm3, triclinic, P(-1), a ) 9.4880(5) Å, b ) 10.3300(4)
Å, c ) 13.0830(6) Å, R ) 101.576(2)°, ꢀ ) 109.730(2)°, γ )
103.089(2)°, V ) 1120.65(9) Å3, Z ) 2, 2θmax ) 58°, collected
(independent) reflections ) 12 415 (5728), Rint ) 0.0426, µ ) 5.260
mm˜1, 276 refined parameters, R1 (for I > 2σ(I)) ) 0.0256, wR21
(for all data) ) 0.0609, max./min. residual electron density ) 1.788/
-1.822 e Ř3.
General Procedure for the Synthesis of Complexes 5 and 6.
To a solution of 208 mg (0.35 mmol) of 3 in 1.5 or 2.8 mL of
toluene was added 1.5 mL (26.5 mmol) of acetaldehyde (5) or 39
µL (0.38 mmol) of benzaldehyde (6), and the reaction mixtures
were stirred at 75 °C for 4 h. The solvents were removed in Vacuo
(ca. 0.01 bar), and the residues were extracted with 15 mL of
petroleum ether. After evaporation the crude product was washed
with n-pentane at -20 °C.
5: colorless solid; yield 152 mg (0.237 mmol, 68%); mp 218 °C
(dec). Selected NMR data: 1H NMR: δ 0.71 (q, J(H,H) ) 1.1 Hz,
3H, Ccage-CH3), 0.89 (s, 3H, Ccage-CH3), 1.30 (d, J(P,H) ) 0.9
Hz, 3H, Ccage-CH3), 1.42 (s, 3H, Ccage-CH3), 1.66 (d, J(H,H) )
6.9 Hz, 3H, C(H)-CH3), 1.71 (q, J(H,H) ) 1.1 Hz, 3H, Ccage-CH3),
2.87 (d, J(P,H) ) 4.5 Hz, 1H, C(H)Ph), 4.66 (dq, J(P,H) ) 3.0 Hz
(d), J(H,H) ) 6.9 Hz (q), 1H, C(H)Me), 7.16-7.37 (mc, 5H, Ph).
13C{1H} NMR: δ 8.8 (s, Ccage-CH3), 11.0 (s, Ccage-CH3), 16.4 (d,
Acknowledgment. Financial support by ThermPhos Int.
AG is gratefully acknowledged.
Supporting Information Available: CIF files giving X-ray
crystallographic data for 3, 5, and 6. This material is available free
of charge via the Internet at http://pubs.acs.org. Crystallographic
data of 3, 5, and 6 have also been deposited at the Cambridge
Crystallographic Data Centre under the numbers CCDC-647516
(3), CCDC-663345 (5), and CCDC-671764 (6). These data can be
obtained free of charge from the Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data _request/cif.
J(P,C) ) 1.9 Hz, Ccage-CH3), 16.9 (d, J(P,C) ) 2.3 Hz, Ccage
-
CH3), 18.4 (d, J(P,C) ) 2.3 Hz, C(H)CH3), 18.7 (d, J(P,C) ) 4.2
Hz, Ccage-CH3), 49.0 (d, J(P,C) ) 22.3 Hz, Ccage), 54.3 (d, J(P,C)
) 4.2 Hz, Ccage), 54.7 (d, J(P,C) ) 21.7 Hz, C(H)Ph), 74.9 (d,
J(P,C) ) 6.8 Hz, C(H)CH3), 93.2 (d, J(P,C) ) 6.5 Hz, Ccage), 126.2
(d, J(P,C) ) 1.6 Hz, Ph (C21/23)), 127.1 (s, p-Ph (C22)), 127.5
(d, J(P,C) ) 1.3 Hz, Ph), 129.3 (d, J(P,C) ) 9.4 Hz, Ph), 130.9 (d,
OM7012953