Electronic structure and evolution of a terminal butadienylphosphinidene complex

Article abstract of DOI:10.1021/om060156t

The DFT study of the 1-butadienylphosphinidene complex [CH ₂=CHCH=CHP-Cr(CO)₅] shows a delocalized structure with a short P-C bond at 1.789 A and a long C_α=C _β double bond at 1.367 A. The W(CO)₅ complex has been synthesized by copper-catalyzed decomposition of the appropriate 7-phosphanorbornadiene complex. It gives the normal reaction products with alkynes (phosphirenes) and with conjugated dienes (phospholenes and dihydrophosphepines via a phospha-Cope rearrangement), but when no trapping reagent is added to the reaction mixture, it gives a complex pentacyclic product whose structure has been established by X-ray crystal structure analysis and whose formation involves a cascade of reactions starting at the dienyl substituent of the precursor.

Full text of DOI:10.1021/om060156t

3152
Organometallics 2006, 25, 3152-3155
Electronic Structure and Evolution of a Terminal
Butadienylphosphinidene Complex
Ngoc Hoa Tran Huy,*,† Shaojie Hao,† Louis Ricard,† and Franc¸ois Mathey*,‡
Laboratoire “He´te´roe´le´ments et Coordination”, UMR CNRS 7653, DCPH, Ecole Polytechnique,
91128 Palaiseau Cedex, France, and UCR-CNRS Joint Research Chemistry Laboratory, Department of
Chemistry, UniVersity of California, RiVerside, California 92521-0403
ReceiVed February 17, 2006
The DFT study of the 1-butadienylphosphinidene complex [CH2dCHCHdCHP-Cr(CO)5] shows a
delocalized structure with a short P-C bond at 1.789 Å and a long CRdCâ double bond at 1.367 Å. The
W(CO)5 complex has been synthesized by copper-catalyzed decomposition of the appropriate 7-phos-
phanorbornadiene complex. It gives the normal reaction products with alkynes (phosphirenes) and with
conjugated dienes (phospholenes and dihydrophosphepines via a phospha-Cope rearrangement), but when
no trapping reagent is added to the reaction mixture, it gives a complex pentacyclic product whose structure
has been established by X-ray crystal structure analysis and whose formation involves a cascade of reactions
starting at the dienyl substituent of the precursor.
Introduction
The electrophilic terminal phosphinidene complexes [RP-
M(CO)5] (M ) Cr, Mo, W) are known to have an electronic
structure which resembles that of singlet carbenes.1 Their LUMO
is essentially the empty pz orbital at phosphorus. Any π-system
directly bonded to phosphorus will stabilize the phosphinidene
by interaction with the pz orbital. From this standpoint, the high-
lying π-electrons of a conjugated dienyl unit would be especially
interesting as a stabilizing unit. From another standpoint, the
reaction of conjugated dienes with phosphinidene complexes
has been one of the most thoroughly studied reactions of
phosphinidenes.2 One can wonder through what kind of reaction
a butadienylphosphinidene complex would evolve toward a
stable compound. These two reasons led us to investigate the
electronic structure and the trapping of these previously
unreported species.
Figure 1. Computed structure of the (butadienylphosphinidene)-
pentacarbonylchromium complex 1. Significant bond lengths
(Å) and angles (deg): P1-Cr2 ) 2.305, P1-C13 ) 1.789, C13-
C15 ) 1.367, C15-C17 ) 1.445, C17-C19 ) 1.346; Cr2-P1-
C13 ) 112.0.
Results and Discussion
complexes adopt a staggered conformation of the P-R and Cr-
(CO)5 units, and the R-P-Cr bond angles are identical.
However, the P-C bond is short in 1 at 1.789 Å vs 1.864 Å
for the P-Me complex and the CRdCâ double bond is long at
1.367 Å vs 1.346 Å for the terminal double bond. As expected,
To evaluate the effect of the introduction of a butadienyl
substituent in [RP-M(CO)5], we performed DFT calculations3
on [(E)-CH2dCHCHdCHP-Cr(CO)5] (1) using the B3LYP
functional4,5 with 6-31G(d) basis sets for all atoms except Cr
(lanl2dz). Our results were then compared to those obtained
for [MeP-Cr(CO)5] at the same level of formalism.6 The
computed structure of 1 is shown in Figure 1. The replacement
of the methyl group by a butadienyl substituent induces some
significant changes in the geometry of the complex. Both
(3) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb,
M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K.
N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.;
Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.;
Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.;
Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li,
X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.;
Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.;
Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.;
Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich,
S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A.
D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A.
G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.;
Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham,
M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.;
Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian
03, revision B.05; Gaussian, Inc.: Wallingford, CT, 2004.
† Ecole Polytechnique.
‡ University of California.
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Streubel, R.; Schoeller, W. W. J. Organomet. Chem. 2002, 643-644, 223.
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10.1021/om060156t CCC: $33.50 © 2006 American Chemical Society
Publication on Web 05/26/2006

A Terminal Butadienylphosphinidene Complex
Organometallics, Vol. 25, No. 13, 2006 3153
not observed in previous experiments with a 1-(tetramethyl-
cyclopentadienyl)phosphole.9 In this case, DMAD reacts with
both the phosphole and cyclopentadiene rings.
Complex 4 shows the characteristic deshielding of the 31P
resonance at 205 ppm (CH2Cl2) and the characteristic 13C
resonance for the terminal dCH2 group at 123.19 ppm (CDCl3).
To check that 4 was a genuine precursor of the butadienylphos-
phinidene complex 5, we investigated the reaction of 4 with
diphenylacetylene at 60 °C in the presence of CuCl as a catalyst.
We obtained the expected phosphirene 6, thus demonstrating
the formation of 5, together with an unknown biphosphorus
compound (7), characterized by two singlet resonances at 48
and 148.6 ppm (eq 3). We shall discuss the structure of 7 later.
Figure 2. Frontier orbitals of 1.
the Cr-P-C4 unit of 1 is strictly planar. These data suggest a
strong conjugation between phosphorus and the vicinal double
bond in 1. The NBO charges confirm this point. The charge at
P is reduced at 0.534 e vs 0.60 e for P-Me. The two double
bonds are highly polarized: CR, -0.606; Câ, -0.131; Cγ,
-0.268; Cδ, -0.333. Thus, it appears that 1 is better represented
by a mesomeric formulation as shown in eq 1.
The phosphirene displays the characteristic shielding of its
31P resonance at -163.8 ppm (CDCl3) and the terminal dCH2
group at 122.91 ppm (CDCl3). The reaction of 4 with 2,3-
dimethylbutadiene was much faster and did not produce the
byproduct 7. The minor product was the phospholene 8 and
the major product the bicyclic compound 9 (eq 4).
The orbital scheme confirms the strong delocalization within
the phosphinidene unit. HOMO-1 is essentially the antibonding
combination of the pz orbital at P and the Ψ2 orbital of
butadiene, the HOMO is still essentially the lone-pair orbital at
P but is destabilized by 0.19 eV by comparison with the P-Me
complex, and the LUMO is heavily localized at P, Câ, and Cδ
(Figure 2).
Our starting synthetic point was the 1-chlorobutenylphosphole
complex 2, whose preparation has been described in a previous
work.7 The dehydrochlorination of the chlorobutenyl substituent
by a strong base afforded the butadienylphosphole complex 3
in good yield (eq 2). The 13C NMR spectrum of 3 shows a
The 13C spectrum of the phospholene 8 shows the intracyclic
CH2 groups as a doublet at 44.48 ppm (1JC-P ) 29.2 Hz) and
the terminal CH2 group as a singlet at 122.2 ppm. The formula
of 9 was established by an X-ray crystal structure analysis
(Figure 3). The origin of 8 and 9 is quite clear. The initial
product is very likely the phosphirane 10, which ring-expands
either via a 1,3-shift to give the phospholene according to a
well-known scheme2 or via a phospha-Cope10a rearrangement
to give a seven-membered ring with a PdC double bond that
reacts with a second molecule of diene to give the bicyclic
compound 910b (eq 5).
characteristic resonance for the terminal dCH2 group as a singlet
at 122.38 ppm (CDCl3). The stereochemistry of the exocyclic
PCHRdCHâ unit was established by inspection of the 1H NMR
spectrum: HR appears as a pseudo-triplet (JH-H ) JH-P ) 16.3
Hz) only compatible with the E stereochemistry.8 Contrary to
what we feared, the Diels-Alder reaction of 3 with dimethyl
acetylenedicarboxylate (DMAD) exclusively took place at the
cyclic diene to give the 7-phosphanorbornadiene complex 4,
once again in good yield (eq 2). Such a perfect selectivity was
(7) Tran Huy, N. H.; Gryaznova, T. V.; Ricard, L.; Mathey, F.
Organometallics 2005, 24, 2930.
(8) Nelson, J. H. Nuclear Magnetic Resonance Spectroscopy; Prentice
Hall: Upper Saddle River, NJ, 2003; p 161.
(9) Frison, G. Ph.D. Thesis, Paris VI University, November 13, 2000.
(10) (a) Appel, R.; Kochta, J.; Winkhaus, V. Chem. Ber. 1988, 121, 631.
(b) Tran Huy, N. H.; Marinetti, A.; Ricard, L.; Mathey, F. Organometallics
1992, 11, 1438.

3154 Organometallics, Vol. 25, No. 13, 2006
Tran Huy et al.
Figure 4. X-ray crystal structure of complex 7. Thermal ellipsoids
are scaled to enclose 50% of the electronic density. Main bond
lengths (Å) and angles (deg): W(1)-P(1) ) 2.4957(8), W(2)-
P(2) ) 2.467(1), P(1)-C(1) ) 1.849(3), P(1)-C(4) ) 1.874(3),
P(1)-C(11) ) 1.886(3), P(2)-O(7) ) 1.653(2), P(2)-C(9) )
1.856(3), P(2)-C(14) ) 1.833(4); C(1)-P(1)-C(4) ) 80.8(1),
C(1)-P(1)-C(11) ) 103.9(1), C(4)-P(1)-C(11) ) 107.4(1),
O(7)-P(2)-C(9) ) 103.1(1), O(7)-P(2)-C(14) ) 102.6(1), C(9)-
P(2)-C(14) ) 105.3(2).
Figure 3. X-ray crystal structure of complex 9. Thermal ellipsoids
are scaled to enclose 50% of the electronic density. Main bond
lengths (Å) and angles (deg): P(1)-W(1) ) 2.5187(6), P(1)-C(1)
) 1.826(2), P(1)-C(5) ) 1.842(2), P(1)-C(10) ) 1.844(2); C(1)-
P(1)-C(10) ) 105.5(1), C(5)-P(1)-C(10) ) 106.8(1), C(1)-
P(1)-C(5) ) 98.1(1), C(4)-C(5)-C(6) ) 111.6(2).
Experimental Section
NMR spectra were recorded on a multinuclear Bruker AVANCE
The formation of 8 and 9 demonstrated that the reaction of
the butadienylphosphinidene 5 toward a conjugated diene was
similar to that of a vinylphosphinidene complex.10b We were
ready then to study the generation and evolution of 5 in the
absence of additional reagent. Upon heating in the presence of
CuCl as a catalyst, the phosphanorbornadiene 4 gave the already
observed biphosphorus compound 7 as the single major product
(eq 6).
1
300 MHz spectrometer operating at 300.13 for H, 75.47 for 13C,
and 121.50 MHz for 31P. Chemical shifts are expressed in parts
per million (ppm) downfield from internal tetramethylsilane (1H
and 13C) and external 85% aqueous H3PO4 (31P). Elemental analyses
were performed by the SerVice de microanalyse du CNRS, Gif-
sur-Yvette, France.
Synthesis of 1-Butadienylphosphole Complex 3. To a solution
of complex 2 (10.5 g, 20 × 10-3 mol) in THF (100 mL) at 0 °C
t
was added BuOK (3 g, 26 × 10-3 mol). The solution was stirred
for 1.5 h. After evaporation of the solvent, the residue was
chromatographed on silica gel with hexane/CH2Cl2 (9/1) as the
eluent. 3 was obtained as a yellow powder, yield 7.3 g (75%).
1
31P NMR (CDCl3): δ 0.9. H NMR (CDCl3): δ 2.42 (s, 6H,
Me), 5.55 (d, 1H, JH-H ) 10 Hz, dCH2), 5.66 (d, 1H, JH-H
)
16.9 Hz, dCH2), 5.98 (pseudo t, 1H, JH-H ) JH-P ) 16.3 Hz,
2
PCHd), 6.58 (d, 2H, JH-P ) 36.7 Hz, ring dCH-P), 6.66 (m,
1H, dCH), 6.95 (m, 1H, dCH). 13C NMR (CDCl3): δ 17.67 (d,
JC-P ) 11.5 Hz, Me), 122.38 (s, dCH2), 123.25 (d, JC-P ) 40.5
Hz, dCHP), 129.45 (d, JC-P ) 44.8 Hz, ring dCHP), 136.36 (d,
JC-P ) 18.8 Hz, dCH), 145.98 (d, JC-P ) 8.6 Hz, dCH),151.42
(d, JC-P ) 9.0 Hz, dCMe), 196.49 (d, JC-P ) 6.7 Hz, cis-CO),
199.45 (d, JC-P ) 27.8 Hz, trans-CO). Anal. Calcd for C15H13O5-
PW: C, 36.91; H, 2.68. Found: C, 37.02; H, 2.64.
Synthesis of 7-Butadienyl-7-phosphanorbornadiene Complex
4. Complex 3 (5 g, 10 × 10-3 mol) and DMAD (3 mL) were heated
overnight at 70 °C in toluene (2 mL). The product was chromato-
graphed on silica gel with hexane/CH2Cl2 (1/1) as the eluent. 4
was obtained as a yellow powder, yield 5 g (80%).
The structure of 7 was established by an X-ray analysis
(Figure 4). On the basis of what we had observed in the reaction
of 5 with dimethylbutadiene, the origin of 7 is very likely the
following. The phosphinidene 5 first reacts with the butadienyl
substituent of a second molecule of precursor 4 to give a seven-
membered ring (11) via a phospha-Cope rearrangement. In 11,
the reactive PdC double bond is close to a CdCCdO unit of
the phosphanorbornadiene. An intramolecular [4 + 2] cycload-
dition takes place between the phosphaalkene and the R,â-
unsaturated ester to give the pentacyclic product 7 in fair yield.
31P NMR (CH2Cl2): δ 205.4. 1H NMR (CDCl3): δ 1.99 (s, 6H,
Me), 3.72 (d, 2H, JH-P ) 1.9 Hz, CH-P), 3.80 (s, 6H, OMe), 5.33
(d, 1H, JH-H ) 9.1 Hz, CH2), 5.42 (d, 1H, JH-H ) 16.1 Hz, CH2),
6.14 (pseudo t, 1H, JH-H ) JH-P ) 16.2 Hz, PCHd), 6.35-6.46
(m, 2H, dCH). 13C NMR (CDCl3): δ 16.24 (d, JC-P ) 2.3 Hz,
Me), 52.82 (s, OMe), 60.47 (d, JC-P ) 21.5 Hz, CHP), 123.19 (s,
This complex and subtle chemistry once again demonstrates
the extraordinary versatility of the phosphole-phosphanorbor-
nadiene route to electrophilic terminal phosphinidene com-
plexes.11
dCH2), 131.47 (d, JC-P ) 10.1 Hz, dCH), 136.33 (d, JC-P
)
13.4 Hz, dCH), 138.45 (d, JC-P ) 17.0 Hz, dC(Me)), 144.71 (d,
JC-P ) 5.4 Hz, dCH), 146.27 (d, JC-P ) 4.6 Hz, dC(CO2Me)),
165.39 (d, JC-P ) 2.8 Hz, CO2), 196.20 (d, JC-P ) 6.8 Hz, cis-
CO), 198.43 (d, JC-P ) 25.4 Hz, trans-CO).
(11) Reviews: (a) Mathey, F.; Tran Huy, N. H.; Marinetti, A. HelV. Chim.
Acta 2001, 84, 2938. (b) Lammertsma, K.; Vlaar, M. J. M. Eur. J. Org.
Chem. 2002, 4, 1127.

A Terminal Butadienylphosphinidene Complex
Organometallics, Vol. 25, No. 13, 2006 3155
Synthesis of 1-Butadienylphosphirene Complex 6. Complex
4 (0.64 g, 1 × 10-3 mol), diphenylacetylene (0.2 g, 1.2 × 10-3
mol), and CuCl (0.03 g) were heated overnight at 60 °C in toluene
(8 mL). The crude product was chromatographed on silica gel with
hexane/CH2Cl2 (9/1) as the eluent. The phosphirene complex 6 was
thus obtained (0.06 g, 25%). Complex 7 was then eluted with
hexane/CH2Cl2 (2/3), yield 0.15 g, 40%.
2.7 Hz, Me), 38.61 (s, OMe), 41.05 (d, JC-P ) 10.3 Hz, P-CH2),
51.71 (d, JC-P ) 21.2 Hz, P-CH), 53.76 (d, JC-P ) 7.7 Hz, OMe),
54.12 (dd, JC-P ) 21.3 and 5.8 Hz, P-CH), 55.18 (s, P-CH), 56.28
(s, P-CH), 56.50 (d, JC-P ) 18.6 Hz, P-CH), 74.96 (s, C), 98.32
(d, JC-P ) 8.7 Hz, dC), 118.37 (s, dCH2), 122.94 (dd, dCH),
123.62 (s, dCH), 133.40 (d, JC-P ) 10.5 Hz, dCMe), 138.75 (d,
JC-P ) 14.6 Hz, dCMe), 141.13 (d, JC-P ) 14.7 Hz, vinyl dCH),
152.52 (s, dCOO), 172.76 (s, CO2Me), 195.75 (d, JC-P ) 7.6 Hz,
1
Data for 6 are as follows. 31P NMR (CDCl3): δ -163.8. H
NMR (CDCl3): δ 5.32 (d, 1H, JH-H ) 9.8 Hz, dCH2), 5.43 (d,
cis-CO), 196.26 (d, JC-P ) 6.8 Hz, cis-CO), 197.89 (d, JC-P )
1H, JH-H ) 16.9 Hz, dCH2), 5.69 (pseudo t, 1H, JH-H ) JH-P
)
27.0 Hz, trans-CO), 198.91 (d, JC-P ) 28.6 Hz, trans-CO), 197.89
(d, JC-P ) 27.0 Hz, trans-CO). Anal. Calcd for C30H24O14P2W2:
C, 34.71; H, 2.33. Found: C, 34.53; H, 2.36.
16.6 Hz, PCHd), 6.38 (m, 1H, dCH), 6.79 (m, 1H, dCH). 13C
NMR (CDCl3): 122.91 (s, dCH2), 127.90 (d, JC-P ) 6.7 Hz,
dC-), 129.19 (d, JC-P ) 8.5 Hz, dC-), 129.67 (s, dCH(Ph)),
130.63 (d, JC-P ) 5.5 Hz, dCH(Ph)), 130.95 (s, dCH(Ph)), 134.65
(d, JC-P ) 6.3 Hz, dCH), 135.65 (d, JC-P ) 19.8 Hz, dCH), 147.68
(d, JC-P ) 13.7 Hz, dCH), 196.22 (d, JC-P ) 8.6 Hz, CO), 198.22
(d, JC-P ) 30.5 Hz, CO). Mass spectrum (184W): m/z 586 (M, 14%),
446 (M - 5CO, 100%).
X-ray Structure Data. General details are as follows: Nonius
Kappa CCD diffractometer, φ and ω scans, Mo KR radiation (λ )
0.710 73 Å), graphite monochromator, T ) 150 K, structure solution
with SIR97,12 refinement against F2 in SHELXL9713 with aniso-
tropic thermal parameters for all non-hydrogen atoms, calculated
hydrogen positions with riding isotropic thermal parameters.
Data collection for 7: colorless plate, 0.20 × 0.14 × 0.12 mm;
monoclinic, P21/c, a ) 17.0670(10) Å, b ) 13.4710(10) Å, c )
16.3210(10) Å, â ) 115.1700(10)°; V ) 3396.1(4) Å3, Z ) 4,
Synthesis of 1-Butadienylphospholene Complex 8 and Bicyclic
Complex 9. Complex 4 (0.32 g, 0.5 × 10-3 mol), 2,3-dimethyl-
butadiene (0.5 mL), and CuCl (0.02 g) were heated for 2 h at 58
°C in toluene (5 mL). The crude product was chromatographed on
silica gel with hexane/CH2Cl2 (9.5/0.5) as the eluent. The phos-
pholene complex 8 was first recovered (0.02 g, 8%) and then the
bicyclic complex 9 (0.1 g, 35%).
Fcalcd ) 2.030 g cm-3, µ ) 6.930 cm-1, F(000) ) 1976, θmax
)
30.03°, hkl ranges -24 to +24, -18 to +16, -22 to +22, 16 351
data collected, 9903 unique data (Rint ) 0.0256), 7814 data with
I > 2σ(I), 437 parameters refined, GOF(F2) ) 1.008, final R indices
(R1 ) ∑||Fo| - |Fc||/∑|Fo|, wR2 ) [∑w(Fo2 - Fc2)2/∑w(Fo2)2]1/2),
R1 ) 0.0290, wR2 ) 0.0693, maximum/minimum residual electron
Data for 8 are as follows. 31P NMR (CDCl3): δ -12.1. 1H NMR
(CDCl3): δ 1.75 (s, 6H, Me), 2.74-2.98 (m, 4H, CH2P), 5.31 (d,
1H, JH-H ) 9.8 Hz, dCH2), 5.40 (d, 1H, JH-H ) 16.8 Hz, dCH2),
6.03 (pseudo t, 1H, JH-H ) JH-P ) 15.8 Hz, dCHP), 6.43 (m, 1H,
density +1.300(0.142)/-1.512(0.142) e Å-3
.
Data collection for 9: colorless plate, 0.20 × 0.20 × 0.14 mm;
triclinic, P1h, a ) 8.3200(10) Å, b ) 10.2930(10) Å, c ) 14.1890-
(10) Å, R ) 91.3990(10)°, â ) 95.9020(10)°, γ ) 112.7390(10)°,
V ) 1112.00(19) Å3, Z ) 2, Fcalcd ) 1.709 g cm-3, µ ) 5.293
cm-1, F(000) ) 560, θmax ) 29.99°, hkl ranges -11 to +11, -14
to +14, -19 to +19, 9450 data collected, 6434 unique data
(Rint ) 0.0190), 6049 data with I > 2σ(I), 257 parameters refined,
GOF(F2) ) 1.058, final R indices (R1 ) ∑||Fo| - |Fc||/∑|Fo|,
wR2 ) [∑w(Fo2 - Fc2)2/∑w(Fo2)2]1/2), R1 ) 0.0241, wR2 ) 0.0629,
maximum/minimum residual electron density +1.113(0.113)/-
dCH), 6.58 (m, 1H, dCH). 13C NMR (CDCl3): 16.53 (d, JC-P
)
7.9 Hz, Me), 44.48 (d, JC-P ) 29.2 Hz, CH2P), 122.21 (s, dCH2),
130.15 (s, dC(Me)), 130.61 (d, JC-P ) 35.4 Hz, dCHP), 136.28
(d, JC-P ) 17.0 Hz, dCH), 143.46 (d, JC-P ) 7.5 Hz, dCH), 197.06
(d, JC-P ) 7,2 Hz, CO). Mass spectrum (CI, NH3; 184W): m/z 491
(M + H, 76%), 436 (100%).
Data for 9 are as follows. 31P NMR (CDCl3): δ -23.2. 1H NMR
(CDCl3): δ 1.60 (s, 3H, Me), 1.73 (s, 3H, Me), 1.75 (s, 6H, Me),
4.95 (d, 1H, JH-H ) 16.9 Hz, dCH2), 5.03 (d, 1H, JH-H ) 10.0
Hz, dCH2), 5.59 (m, 1H, dCH). 13C NMR (CDCl3): 20.49 (s,
Me), 21.10 (d, JC-P ) 2.1 Hz, Me), 22.20 (d, JC-P ) 8.0 Hz, Me),
22.66 (d, JC-P ) 2.9 Hz, Me), 28.69 (d, JC-P ) 26.0 Hz, CH2),
1.575(0.113) e Å-3
.
Acknowledgment. We thank the Ecole Polytechnique, the
CNRS, and the University of California Riverside for financial
support of this work.
36.32 (s, CH2), 39.52 (d, JC-P ) 19.8 Hz, CH2), 41.38 (d, JC-P
)
3.6 Hz, CH), 41.93 (s, CH2), 42.10 (d, JC-P ) 19.5 Hz, CH-P),
115.01 (s, dCH2), 120.84 (d, JC-P ) 3.5 Hz, dC-), 125.30 (d,
JC-P ) 10.2 Hz, dC-), 126.05 (d, JC-P ) 11.5 Hz, dC-), 133.39
(d, JC-P ) 6.5 Hz, dC-), 143.33 (d, JC-P ) 8.6 Hz, dCH). Mass
spectrum (CI, NH3; 184W): m/z 572 (M, 100%). Anal. Calcd for
C21H25O5PW: C, 44.08; H, 4.39. Found: C, 43.91; H, 4.39.
Synthesis of the Polycyclic Complex 7 by Thermolysis of the
7-Butadienyl-7-phosphanorbornadiene Complex 4. Complex 4
(1 g, 1.58 × 10-3 mol) and CuCl (0.03 g) were heated for 3 h at
58 °C in toluene (8 mL). The crude product was chromatographed
on silica gel with hexane/CH2Cl2 (1/1) as the eluent. Complex 7
was recovered as yellow crystals (0.4 g, 50%).
Supporting Information Available: CIF files giving data for
the X-ray crystal structure analyses of complexes 7 and 9. This
material is available free of charge via the Internet at http://
pubs.acs.org.
OM060156T
(12) Altomare, A.; Burla, M. C.; Camalli, M.; Cascarano, G.; Giacovazzo,
C.; Guagliardi, A.; Moliterni, A. G. G.; Polidori, G.; Spagna, R. SIR97, an
integrated package of computer programs for the solution and refinement
of crystal structures using single-crystal data.
(13) Sheldrick, G. M. SHELXL-97; Universita¨t Go¨ttingen, Go¨ttingen,
Germany, 1997.
Data for 7 are as follows. 31P NMR (CDCl3): δ 48.0, 148.6. 13
NMR (CDCl3): δ 14.83 (d, JC-P ) 3.7 Hz, Me), 15.28 (d, JC-P
C
)