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The Ramirez yl­ide undergoes electrophilic substitution with di­alkyl acetyl­ene­di­carboxyl­ates, yielding a mixture of the Z and E adducts. The crystal structure analyses of the two adducts formed using di­methyl­acetyl­ene, viz. di­methyl (E)- and (Z)-1-[2-(tri­phenyl­phospho­ranyl­idene)­cyclo­pentadien-1-yl]­ethyl­ene­di­carboxyl­ate, both C29H25O4P, explain an unusual chemical shift observed for the vinyl H atom of the Z adduct, which had previously precluded a definitive assignment of the isomers. In addition, the structures explain why only one of the isomers reacts further with acetyl­ene esters to produce azulenes with a rare substitution pattern.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104006067/fa1050sup1.cif
Contains datablocks global, IIIa, IIIb

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104006067/fa1050IIIasup2.hkl
Contains datablock IIIa

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104006067/fa1050IIIbsup3.hkl
Contains datablock IIIb

CCDC references: 224866; 224867

Comment top

The ylide cyclopentadien-1-ylidetriphenylphosphorane, (I) [often referred to as the Ramirez ylide], is known to be unreactive in the Wittig reaction on account of the aromaticity present in the five-membered ring (Ramirez & Levy, 1957a,b). Instead, as shown by Yoshida et al. (1971a,b, 1973), (I) reacts towards electrophiles, undergoing substitution at the 2-position. In one case, an activated acetylene (diethyl acetylene dicarboxylate) was used, which gave a putative vinyl adduct, (II), but the stereochemistry of the double bond was not established. We had cause to reinvestigate this reaction and we extended the study to other dialkylacetylenic esters (R=Me, Et and tBu). The reactions typically gave two isomeric adducts, one of which exhibits an unusual chemical shift (4.7 p.p.m.) in the 1H NMR spectrum. This behaviour precluded a definitive E/Z assignment of the isomers.

In addition, we have found that one isomer in each case reacts with further acetylene ester to give azulenes with a rare subtitution pattern (Higham et al., 2004). It was clear that an X-ray crystallographic study would identify the isomer stereochemistry, shed light on the unusual chemical shift and provide valuable information as to why only one isomer should react to form azulenes. To this end, we reacted (I) with dimethylacetylene dicarboxylate and isolated the major isomer by recrystallization. An X-ray crystallographic study proved this to be, somewhat surprisingly, the Z adduct, (IIIa) (Fig. 1).

The approximate planarity of the five-membered ring and the alkene function, together with the short distance [1.438 (2) Å] between atoms C2 and C6, suggests conjugation of the new alkene with the cyclopentadienyl ring. It is also clear that the vinyl H atom is in an unusual location, placing it within the bonding domain of the ylide bond (an ylide pocket), that provides some explanation, together with the extensive conjugation present, as to the unusual chemical shift of 4.71 p.p.m. We calculate the shortened contact distance between atom P1 and the vinyl H atom attached to atom C9 to be 2.81 (2) Å. The latter (the unusual H-atom position?) might be thought of as a factor in the elongation of the C1—C2 bond [1.4496 (19) Å] relative to the C1—C5 bond length [1.411 (2) Å]. On the other hand, there is also substantial elongation of the C1—C2 bond in the other adduct (see next section) and in the Ramirez ylide itself (see below; the internuclear P···H distance is 2.71 Å, calculated on the basis of an internuclear C—H distance of 1.08 Å).

The spectroscopic data for the minor product were consistent with a species formed quantitatively when dichloromethane solutions of (IIIa) were subjected to a source of ultraviolet light for 96 h (this process could not be duplicated by prolonged heating). Recrystallization from dichloromethane/ethanol yielded orange crystals, which when analysed by X-ray crystallography were found to be the E-isomer (IIIb) (Fig. 2). In contrast to (IIIa), there is a high steric hindrance inherent in (IIIb), which twists the alkene and five-membered ring out of the same plane by 43.3 (2)°, and the C2—C6 bond length increases to 1.464 (3) Å, concomitant with the associated loss of electron delocalization. The 1H NMR spectrum supports this result in giving a chemical shift closer to that expected for vinyl protons [6.29 p.p.m. compared to 4.71 p.p.m. in (IIIa)]. Pertinent bond lengths and angles for (I), (IIIa) and (IIIb) are given in Table 1 [see Ammon et al. (1973) for comprehensive structural details of (I)].

It is striking that the bond lengths within the five-membered rings of (I), (IIIa) and (IIIb) are consistently unequal. Thus the C1—C2 and C4—C5 bonds are both elongated, while the C3—C4 bond is truncated compared with the C1—C5 and C2—C3 bonds. It is not clear why the bond length inequalities in the adducts (which might be expected) should also be reflected in the parent, and we assume that this behaviour is a coincidence. The P—C1 bond lengths should be more informative, being related to the nature of the ylide bond, and it is notable that, in the adducts, these bonds are elongated [1.7412 (14) Å for (IIIa), 1.7357 (18) Å for (IIIb) and 1.718 (2) Å for (I)]. Ordinarily this would mean (Gilheany, 1994) that the ylide carbanion in the adducts is more delocalized than in the parent. However, this conclusion is not consistent with the lack of coplanarity between the five-membered ring and the vinyl substituent in (IIIb). It is also noteworthy that the external C2—C1—P angle is wider in the adducts [131.86 (11)° for (IIIa), 130.43 (14)° for (IIIb) and 125.3 (2)° for (I)].

We were also interested in the details of the conformation of the ylide portion of the molecules. It is frequently observed in X-ray studies that the carbanion substituents tend to take up an orientation at right-angles to the plane of one of the P-substituent bonds, referred to as the unique substituent. This behaviour is illustrated in Fig. 3, the conformation being called perpendicular. In addition, it is common that a deviation from carbanion planarity occurs, of up to 20° from the plane perpendicular to the plane containing the PC bond and the unique substituent. Where there is a deviation, it is usually towards the unique substituent, the P—C bond length of which is, in turn, lengthened. These observations are linked to the electronic structure of a typical phosphonium ylide (Gilheany, 1994), where there is overlap of the occupied p-orbital on the carbanion into an antibonding orbital of the phosphorus substituent (called negative hyperconjugation). Therefore, it is notable that in both adducts there is no such deviation from planarity and no evidence that one of the P—C(Ph) bonds is unique.

The bond lengths, X-ray photoelectron spectra and 1H-1H coupling constants previously obtained for the Ramirez ylide have been used to describe the amount of ylide–ylene character present (86% ylide), but this two-component bonding description has since fallen out of favour (Gilheany, 1994). It is sufficient to note for (IIIa) and (IIIb) that the increased P—C1 bond length and C2—C1—P bond angle suggest less ylene character than may be present in the parent compound. The bond lengths and angles within the PPh3 group for the three compounds are as expected and unremarkable.

In conclusion, X-ray crystallographic studies of (IIIa) and (IIIb) have allowed the stereochemical assignment of the vinyl adducts. When diethyl and di-tert-butylacetylene dicarboxylate were reacted with (I), a mixture of the Z and E isomers were again obtained in each case. A 1H NMR resonance at 4.7 p.p.m. was observed in both reactions and assigned to the Z adduct on account of the previous discussion. Therefore, the adduct initially reported by Yoshida can now confidently be said to have Z stereochemistry. Our mechanistic studies of the formation of azulenes (Higham et al., 2004) reveal a step that is dependent on a Wittig reaction, and this is only feasible for the E isomer (IIIb). For the Z isomer (IIIa), this study illustrates why no reaction takes place, namely because no rotation of the vinyl bond can bring the phosphorus and the requisite β-carbonyl group into close enough proximity.

Experimental top

For the preparation of (IIIa), dimethylacetylene dicarboxylate (0.43 g, 3.0 mmol) was added to a foil-enclosed solution of (I) (1.0 g, 3.0 mmol) in benzene (30 ml) and stirred overnight under nitrogen. The yellow precipitate was filtered off and stored, and the filtrate was evaporated, yielding a solid that, when triturated with hot methanol, gave a fine yellow powder. Both solids were identical by 1H NMR analysis and were combined. Recrystallization from carbon tetrachloride/ethanol yielded crystals suitable for a crystallographic study. Yield 0.86 g, 60%; m.p. 517–518 K. For the preparation of (IIIb), the phosphorane (IIIa) (1.0 g, 2.14 mmol) was dissolved in dichloromethane (40 ml) in a 50 ml Pyrex roundlbottomed flask under nitrogen. The flask was placed 15 cm from the UV source (300 W lamp) and irradiated for 96 h. The wine-coloured solution was evaporated and the resulting brown–orange solid was recrystallized from dichloromethane/ethanol in a darkened flask, giving orange crystals. Yield 0.9 g, 90%; m.p. 507–508 K.

Refinement top

Crystals of (IIIa) are monoclinic and space group P2(1)/n was chosen from the systematic absences. Crystals of (IIIb) are orthorhombic and space group Pbca was chosen from the systematic absences. All H atoms were located in a difference Fourier map and their positional and isotropic displacement parameters were allowed to refine independantly. Refined C—H distances in (IIIa) are in the range 0.89 (2)–1.01 (2) Å, and refined C—H distances in (IIIb) are in the range 0.89 (4)–1.05 (4) Å, with individual standard deviations of between 0.02 and 0.04 Å.

Computing details top

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2002) and ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecule of (IIIa); displacement ellipsoids are drawn at the 40% probability level.
[Figure 2] Fig. 2. The molecule of (IIIb); displacement ellipsoids are drawn at the 40% probability level.
[Figure 3] Fig. 3. The ylide bonding model, in which `Ru' represents the unique substituent.
(IIIa) dimethyl (Z)-1-[2-(triphenylphosphoranylidene)cyclopentadien-1-yl]ethylenedicarboxylate top
Crystal data top
C29H25O4PF(000) = 984
Mr = 468.46Dx = 1.259 Mg m3
Monoclinic, P21/nMelting point: 517 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 13.7622 (15) ÅCell parameters from 5590 reflections
b = 11.8849 (13) Åθ = 2.3–26.3°
c = 15.8788 (17) ŵ = 0.14 mm1
β = 107.914 (2)°T = 293 K
V = 2471.3 (5) Å3Prism, brown
Z = 40.50 × 0.40 × 0.36 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
6129 independent reflections
Radiation source: fine-focus sealed tube5100 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
ϕ and ω scansθmax = 28.3°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
h = 1818
Tmin = 0.877, Tmax = 0.950k = 1515
43496 measured reflectionsl = 2121
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: difference Fourier map
wR(F2) = 0.127All H-atom parameters refined
S = 1.05 w = 1/[σ2(Fo2) + (0.068P)2 + 0.5453P]
where P = (Fo2 + 2Fc2)/3
6129 reflections(Δ/σ)max = 0.005
407 parametersΔρmax = 0.41 e Å3
0 restraintsΔρmin = 0.16 e Å3
Crystal data top
C29H25O4PV = 2471.3 (5) Å3
Mr = 468.46Z = 4
Monoclinic, P21/nMo Kα radiation
a = 13.7622 (15) ŵ = 0.14 mm1
b = 11.8849 (13) ÅT = 293 K
c = 15.8788 (17) Å0.50 × 0.40 × 0.36 mm
β = 107.914 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
6129 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
5100 reflections with I > 2σ(I)
Tmin = 0.877, Tmax = 0.950Rint = 0.027
43496 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.127All H-atom parameters refined
S = 1.05Δρmax = 0.41 e Å3
6129 reflectionsΔρmin = 0.16 e Å3
407 parameters
Special details top

Experimental. Routine 1H and 13C NMR spectra were obtained on a Jeol JNMGX 270 MHz s pectrometer in CDCl3 at 25° C with TMS as internal standard unless otherwise stated. The 31P NMR spectra were recorded under the same conditions on a Varian Unity 300 MHz instrument with 85% orthophosphoric acid as external standard. The lamp used for the UV irradiation experiments was a commercially available 300 W sunlamp. UV/Visible spectra were obtained in 1 cm quartz cells on a Hewlett Packard spectrophotometer. IR spectra (KBr) were recorded on a Mattson Instruments spectrophotometer. Elemental analyses and mass spectra were carried out at UCD. The reactions were carried out under a N2 atmosphere dried by passing it through anhydrous calcium chloride. All commercially available chemicals were used without further purification unless specified. The liquid acetylene dicarboxylates (Aldrich) were stored under N2 and refrigerated. Cyclopentadiene was prepared from technical dicyclopentadiene and used immediately (Furnis et al., 1978). Solvents were dried according to standard procedures (Armerego & Perrin, 1988).

Cyclopentadien-1-ylidenetriphenylphosphorane (1). This was a modification of the Ramirez route. Freshly distilled cyclopentadiene (20.0 ml, 16.5 g, 0.25 mol.) was dissolved in chloroform and cooled to −65° C. Bromine was added slowly to this (12.5 ml, 39.8 g, 0.25 mol) and the temperature kept constant. After 1 h the reaction was allowed to warm to room temperature and was added to a solution of triphenylphosphine (131.1 g, 0.5 mol.) in chloroform (500 ml). After reflux (14 h) the solvent was evaporated to leave a glassy yellow residue, which was redissolved in methanol (1 L). The solution was cooled to 0° C and 10% NaOH was added until the pH was 11. The yellow precipitate generated was filtered and washed with cold water and methanol. In air and light the product becomes discoloured (initially purple and then brown) but can be recrystallized from dichloromethane/ethanol to give a light brown solid. This is redissolved in dichloromethane (150 ml) and heated, and decolourizing charcoal added (10 g). After 5 minutes, hot filtration and evaporation yielded a yellow solid, which does not degrade in air or light. Yield 43.3 g, (53%). Mpt. = 228 − 229° C (Lit. value 225 − 227° C). νmax (KBr): 3080, 1485, 1440, 1435, 1355, 1315, 1230, 1220, 1205, 1185, 1160, 1110, 1105, 1050, 1035, 1000, 760, 730 cm−1. 1H NMR: 7.45–7.97 (m, 15 H, aryl), 6.44–6.49 (m, 2 H, cyclopentadienyl), 6.27–6.31 (m, 2H, cyclopentadienyl) p.p.m.. Z-2-(a,b-Dicarbomethoxyvinyl)cyclopentadien-1-ylidenetriphenylphosphorane (3a). Dimethylacetylene dicarboxylate (0.43 g, 3.0 mmol) was added to a foil-enclosed solution of 1 (1.0 g, 3.0 mmol) in benzene and stirred overnight. The yellow precipitate was filtered and stored and the filtrate was evaporated to give a solid, which when triturated with hot methanol gave a fine yellow powder. Both solids were identical by 1H NMR and were combined. Yield = 0.86 g, (60%). Mpt. = 244 − 245° C. 1H NMR (Varian Unity 300 MHz): 7.71–7.51 (m, 15 H, aryl), 6.74 (m, 1H, cyclopentadienyl), 6.28 (m, 1H, cyclopentadienyl), 5.96, (m, 1H, cyclopentadienyl), 4.71 (s, 1H, vinyl), 3.90 (s, 3H, methyl), 3.34 (s, 3H, methyl) p.p.m.. 13C NMR: 171.0, 167.0, 134.2, 133.7, 133.1, 133.0, 131.0, 129.4, 128.8, 126.5, 126.0, 122.0, 121.7, 120.6, 115.1, 114.5, 114.1, 104.1, 83.5, 51.4, 50.3 p.p.m.. 31P NMR: 14.8 p.p.m.. Anal. Calcd. (found) for C29H25O4P: C, 74.35 (74.08); H, 5.38 (5.70). Mass spectrum: m/z 468 (M+). νmax (KBr): 3075, 2895, 2920 (sh.), 1730 (C=O), 1680–1695 (C=O), 1550–70, 1470, 1440, 1390 (w), 1370, 1350, 1315, 1270, 1220, 1180, 1145, 1105 cm −1. λmax (logε, CH2Cl2): 348 (sh.) (4.37), 395 (4.40), 546 (sh.) (1.07) nm.

Armerego, W. & Perrin, E. (1988). Purification of Laboratory Chemicals. Pergamon Press.

Furnis, B. S. Hannaford, A. J. Rogers, V. Smith, P. W. G. & Tatchell, A. R. (1978). In Vogel's Textbook of Practical Organic Chemistry. London: Longmann.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
P0.36001 (2)0.45424 (3)0.10585 (2)0.03366 (11)
C10.44428 (10)0.56404 (12)0.14933 (9)0.0361 (3)
C20.51978 (10)0.57986 (12)0.23516 (9)0.0380 (3)
C60.54906 (11)0.50831 (14)0.31186 (10)0.0416 (3)
C70.64327 (12)0.54625 (14)0.38425 (10)0.0467 (4)
O10.72897 (9)0.53348 (13)0.38234 (9)0.0658 (4)
O20.61848 (10)0.59874 (12)0.44862 (8)0.0623 (3)
C80.7025 (3)0.6232 (3)0.52702 (17)0.0878 (8)
H8A0.677 (2)0.659 (3)0.565 (2)0.110 (10)*
H8B0.730 (2)0.551 (3)0.552 (2)0.114 (11)*
H8C0.754 (2)0.660 (3)0.512 (2)0.110 (11)*
C90.50509 (12)0.41125 (16)0.32399 (11)0.0489 (4)
H90.4465 (16)0.3850 (16)0.2826 (14)0.062 (6)*
C100.54633 (12)0.33686 (16)0.39943 (11)0.0519 (4)
O30.62264 (10)0.35011 (13)0.46089 (9)0.0702 (4)
O40.48666 (10)0.24428 (12)0.39100 (9)0.0658 (4)
C110.5235 (2)0.1598 (3)0.4578 (3)0.0971 (10)
H11A0.474 (2)0.096 (3)0.441 (2)0.112 (9)*
H11B0.528 (2)0.199 (3)0.513 (2)0.117 (12)*
H11C0.596 (2)0.143 (2)0.4684 (18)0.102 (9)*
C30.56649 (12)0.68421 (13)0.23078 (11)0.0441 (3)
H30.6214 (14)0.7149 (15)0.2789 (12)0.049 (5)*
C40.52258 (13)0.73225 (13)0.14801 (11)0.0462 (4)
H40.5407 (14)0.8039 (16)0.1290 (12)0.055 (5)*
C50.44809 (12)0.65965 (13)0.09778 (10)0.0408 (3)
H50.4079 (13)0.6690 (14)0.0387 (11)0.043 (4)*
C120.26944 (10)0.43751 (13)0.16751 (9)0.0378 (3)
C130.21979 (13)0.33801 (16)0.17251 (14)0.0546 (4)
H130.2306 (18)0.275 (2)0.1408 (15)0.078 (7)*
C140.14795 (14)0.33412 (19)0.21796 (15)0.0639 (5)
H140.1148 (19)0.267 (2)0.2198 (17)0.090 (8)*
C150.12536 (14)0.4282 (2)0.25732 (13)0.0610 (5)
H150.0721 (18)0.425 (2)0.2886 (16)0.086 (7)*
C160.17255 (17)0.5279 (2)0.25170 (15)0.0687 (6)
H160.1617 (19)0.597 (2)0.2820 (17)0.092 (8)*
C170.24555 (15)0.53267 (17)0.20774 (13)0.0560 (4)
H170.2807 (16)0.6021 (18)0.2070 (14)0.064 (6)*
C180.28559 (10)0.48988 (12)0.00584 (9)0.0367 (3)
C190.20409 (14)0.56371 (16)0.01951 (11)0.0526 (4)
H190.1870 (14)0.5942 (16)0.0304 (13)0.056 (5)*
C200.14735 (15)0.59372 (19)0.10497 (12)0.0649 (5)
H200.0921 (18)0.642 (2)0.1113 (15)0.080 (7)*
C210.17119 (15)0.54996 (17)0.17599 (12)0.0581 (5)
H210.1311 (17)0.5719 (19)0.2350 (16)0.077 (6)*
C220.25249 (14)0.47858 (17)0.16307 (11)0.0552 (4)
H220.2707 (15)0.4478 (17)0.2125 (14)0.063 (6)*
C230.31061 (13)0.44874 (15)0.07787 (11)0.0481 (4)
H230.3647 (15)0.3979 (17)0.0694 (13)0.061 (5)*
C240.42244 (11)0.32218 (12)0.10032 (9)0.0380 (3)
C250.36735 (13)0.22951 (14)0.05618 (11)0.0475 (4)
H250.2977 (15)0.2325 (16)0.0297 (12)0.054 (5)*
C260.41773 (17)0.12995 (15)0.05206 (13)0.0586 (5)
H260.3808 (17)0.073 (2)0.0216 (15)0.073 (6)*
C270.52208 (17)0.12216 (16)0.09100 (14)0.0634 (5)
H270.5577 (18)0.054 (2)0.0874 (16)0.080 (7)*
C280.57667 (15)0.21326 (17)0.13281 (13)0.0595 (5)
H280.6445 (18)0.2074 (19)0.1591 (15)0.074 (6)*
C290.52795 (12)0.31423 (14)0.13770 (11)0.0460 (3)
H290.5655 (14)0.3784 (16)0.1659 (12)0.053 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P0.02874 (17)0.03522 (19)0.03332 (18)0.00100 (13)0.00409 (13)0.00289 (13)
C10.0319 (6)0.0369 (7)0.0369 (7)0.0016 (5)0.0067 (5)0.0020 (5)
C20.0340 (6)0.0404 (7)0.0380 (7)0.0019 (5)0.0084 (5)0.0020 (6)
C60.0331 (7)0.0512 (8)0.0366 (7)0.0005 (6)0.0051 (6)0.0014 (6)
C70.0409 (8)0.0555 (9)0.0382 (8)0.0036 (7)0.0039 (6)0.0005 (7)
O10.0363 (6)0.0982 (11)0.0572 (8)0.0068 (6)0.0060 (5)0.0047 (7)
O20.0580 (7)0.0773 (9)0.0427 (6)0.0062 (6)0.0024 (5)0.0120 (6)
C80.0851 (18)0.107 (2)0.0499 (12)0.0072 (17)0.0099 (12)0.0259 (13)
C90.0383 (8)0.0591 (10)0.0408 (8)0.0055 (7)0.0003 (6)0.0102 (7)
C100.0403 (8)0.0630 (10)0.0482 (9)0.0006 (7)0.0074 (7)0.0134 (8)
O30.0512 (7)0.0858 (10)0.0570 (7)0.0034 (7)0.0078 (6)0.0224 (7)
O40.0516 (7)0.0672 (8)0.0691 (8)0.0059 (6)0.0047 (6)0.0283 (7)
C110.0691 (16)0.096 (2)0.113 (2)0.0010 (14)0.0094 (15)0.062 (2)
C30.0422 (8)0.0418 (8)0.0481 (8)0.0060 (6)0.0138 (7)0.0083 (6)
C40.0532 (9)0.0348 (7)0.0551 (9)0.0046 (6)0.0231 (7)0.0009 (7)
C50.0426 (7)0.0391 (7)0.0414 (8)0.0039 (6)0.0141 (6)0.0043 (6)
C120.0310 (6)0.0454 (8)0.0336 (7)0.0003 (5)0.0046 (5)0.0049 (6)
C130.0460 (9)0.0458 (9)0.0750 (12)0.0017 (7)0.0232 (8)0.0102 (8)
C140.0487 (10)0.0633 (12)0.0843 (14)0.0020 (8)0.0274 (9)0.0234 (10)
C150.0460 (9)0.0885 (14)0.0512 (10)0.0017 (9)0.0191 (8)0.0090 (9)
C160.0689 (12)0.0852 (15)0.0617 (12)0.0101 (11)0.0342 (10)0.0209 (11)
C170.0587 (10)0.0601 (11)0.0544 (10)0.0139 (8)0.0251 (8)0.0150 (8)
C180.0314 (6)0.0399 (7)0.0352 (7)0.0013 (5)0.0047 (5)0.0045 (5)
C190.0531 (9)0.0620 (10)0.0412 (8)0.0213 (8)0.0125 (7)0.0070 (7)
C200.0579 (11)0.0807 (14)0.0516 (10)0.0319 (10)0.0100 (8)0.0188 (9)
C210.0574 (10)0.0718 (12)0.0372 (8)0.0110 (9)0.0028 (7)0.0103 (8)
C220.0590 (10)0.0688 (11)0.0360 (8)0.0080 (8)0.0118 (7)0.0005 (7)
C230.0420 (8)0.0601 (10)0.0405 (8)0.0119 (7)0.0102 (6)0.0023 (7)
C240.0371 (7)0.0365 (7)0.0381 (7)0.0037 (5)0.0083 (6)0.0041 (5)
C250.0468 (9)0.0457 (9)0.0483 (8)0.0038 (7)0.0121 (7)0.0033 (7)
C260.0788 (13)0.0410 (9)0.0605 (11)0.0042 (9)0.0282 (10)0.0073 (8)
C270.0800 (13)0.0483 (10)0.0656 (12)0.0217 (9)0.0278 (10)0.0044 (8)
C280.0491 (10)0.0652 (12)0.0606 (11)0.0213 (9)0.0117 (8)0.0061 (9)
C290.0382 (7)0.0483 (9)0.0476 (8)0.0053 (6)0.0074 (6)0.0015 (7)
Geometric parameters (Å, º) top
P—C11.7412 (14)C13—C141.393 (3)
P—C241.8044 (15)C13—H130.94 (2)
P—C181.8045 (14)C14—C151.363 (3)
P—C121.8173 (15)C14—H140.92 (3)
C1—C51.411 (2)C15—C161.368 (3)
C1—C21.4496 (19)C15—H151.01 (2)
C2—C31.409 (2)C16—C171.390 (3)
C2—C61.438 (2)C16—H160.98 (3)
C6—C91.344 (2)C17—H170.96 (2)
C6—C71.513 (2)C18—C231.381 (2)
C7—O11.199 (2)C18—C191.388 (2)
C7—O21.328 (2)C19—C201.388 (2)
O2—C81.444 (2)C19—H190.96 (2)
C8—H8A0.89 (3)C20—C211.370 (3)
C8—H8B0.97 (3)C20—H200.93 (2)
C8—H8C0.93 (3)C21—C221.368 (3)
C9—C101.456 (2)C21—H210.97 (2)
C9—H90.92 (2)C22—C231.389 (2)
C10—O31.204 (2)C22—H220.97 (2)
C10—O41.355 (2)C23—H230.94 (2)
O4—C111.436 (3)C24—C291.393 (2)
C11—H11A1.00 (3)C24—C251.397 (2)
C11—H11B0.98 (3)C25—C261.383 (2)
C11—H11C0.98 (3)C25—H250.922 (19)
C3—C41.389 (2)C26—C271.381 (3)
C3—H30.966 (18)C26—H260.89 (2)
C4—C51.389 (2)C27—C281.368 (3)
C4—H40.961 (19)C27—H270.96 (2)
C5—H50.938 (17)C28—C291.388 (2)
C12—C131.380 (2)C28—H280.90 (2)
C12—C171.387 (2)C29—H290.952 (19)
C1—P—C24113.71 (7)C12—C13—H13119.3 (14)
C1—P—C18108.74 (7)C14—C13—H13120.4 (14)
C24—P—C18106.93 (7)C15—C14—C13120.60 (19)
C1—P—C12110.60 (7)C15—C14—H14120.6 (16)
C24—P—C12110.29 (7)C13—C14—H14118.8 (16)
C18—P—C12106.21 (6)C14—C15—C16120.08 (17)
C5—C1—C2107.29 (12)C14—C15—H15120.2 (14)
C5—C1—P120.84 (11)C16—C15—H15119.7 (14)
C2—C1—P131.86 (11)C15—C16—C17119.9 (2)
C3—C2—C6123.33 (13)C15—C16—H16122.8 (15)
C3—C2—C1105.89 (13)C17—C16—H16117.0 (15)
C6—C2—C1130.76 (13)C12—C17—C16120.58 (18)
C9—C6—C2127.44 (14)C12—C17—H17120.3 (12)
C9—C6—C7117.73 (14)C16—C17—H17119.1 (12)
C2—C6—C7114.76 (13)C23—C18—C19119.32 (14)
O1—C7—O2124.50 (15)C23—C18—P121.33 (11)
O1—C7—C6124.26 (15)C19—C18—P119.29 (12)
O2—C7—C6111.21 (13)C18—C19—C20120.00 (16)
C7—O2—C8115.52 (18)C18—C19—H19119.9 (11)
O2—C8—H8A107 (2)C20—C19—H19120.1 (11)
O2—C8—H8B106.5 (19)C21—C20—C19120.14 (17)
H8A—C8—H8B109 (3)C21—C20—H20122.6 (14)
O2—C8—H8C109.9 (19)C19—C20—H20117.2 (14)
H8A—C8—H8C116 (3)C22—C21—C20120.24 (16)
H8B—C8—H8C107 (3)C22—C21—H21120.6 (14)
C6—C9—C10124.08 (15)C20—C21—H21119.1 (14)
C6—C9—H9121.4 (12)C21—C22—C23120.23 (17)
C10—C9—H9114.4 (12)C21—C22—H22121.2 (12)
O3—C10—O4122.51 (16)C23—C22—H22118.6 (12)
O3—C10—C9127.55 (17)C18—C23—C22120.03 (15)
O4—C10—C9109.92 (14)C18—C23—H23119.9 (12)
C10—O4—C11115.44 (18)C22—C23—H23120.0 (12)
O4—C11—H11A105.8 (18)C29—C24—C25119.62 (14)
O4—C11—H11B103.6 (19)C29—C24—P119.20 (12)
H11A—C11—H11B117 (3)C25—C24—P121.13 (11)
O4—C11—H11C112.1 (17)C26—C25—C24119.70 (16)
H11A—C11—H11C118 (2)C26—C25—H25118.5 (12)
H11B—C11—H11C99 (2)C24—C25—H25121.8 (12)
C4—C3—C2109.65 (14)C27—C26—C25120.24 (18)
C4—C3—H3126.9 (11)C27—C26—H26122.0 (14)
C2—C3—H3123.4 (11)C25—C26—H26117.7 (15)
C5—C4—C3108.51 (14)C28—C27—C26120.30 (17)
C5—C4—H4125.9 (11)C28—C27—H27119.0 (14)
C3—C4—H4125.6 (11)C26—C27—H27120.6 (14)
C4—C5—C1108.65 (14)C27—C28—C29120.58 (18)
C4—C5—H5127.2 (11)C27—C28—H28120.0 (15)
C1—C5—H5124.1 (11)C29—C28—H28119.3 (15)
C13—C12—C17118.71 (15)C28—C29—C24119.53 (16)
C13—C12—P123.95 (13)C28—C29—H29121.1 (11)
C17—C12—P117.25 (12)C24—C29—H29119.4 (11)
C12—C13—C14120.08 (19)
C24—P—C1—C5117.50 (12)C18—P—C12—C1789.34 (14)
C18—P—C1—C51.50 (14)C17—C12—C13—C140.6 (3)
C12—P—C1—C5117.76 (12)P—C12—C13—C14177.02 (14)
C24—P—C1—C261.61 (16)C12—C13—C14—C150.5 (3)
C18—P—C1—C2179.38 (13)C13—C14—C15—C160.7 (3)
C12—P—C1—C263.12 (16)C14—C15—C16—C171.7 (3)
C5—C1—C2—C30.68 (16)C13—C12—C17—C160.4 (3)
P—C1—C2—C3178.53 (12)P—C12—C17—C16176.26 (16)
C5—C1—C2—C6178.87 (15)C15—C16—C17—C121.5 (3)
P—C1—C2—C60.3 (3)C1—P—C18—C2398.62 (14)
C3—C2—C6—C9175.63 (16)C24—P—C18—C2324.55 (15)
C1—C2—C6—C96.5 (3)C12—P—C18—C23142.33 (14)
C3—C2—C6—C77.4 (2)C1—P—C18—C1978.73 (15)
C1—C2—C6—C7170.56 (15)C24—P—C18—C19158.09 (14)
C9—C6—C7—O199.7 (2)C12—P—C18—C1940.32 (15)
C2—C6—C7—O177.6 (2)C23—C18—C19—C201.3 (3)
C9—C6—C7—O282.4 (2)P—C18—C19—C20178.71 (16)
C2—C6—C7—O2100.28 (17)C18—C19—C20—C210.5 (3)
O1—C7—O2—C811.1 (3)C19—C20—C21—C221.6 (3)
C6—C7—O2—C8171.0 (2)C20—C21—C22—C230.9 (3)
C2—C6—C9—C10172.57 (16)C19—C18—C23—C222.0 (3)
C7—C6—C9—C104.4 (3)P—C18—C23—C22179.34 (14)
C6—C9—C10—O30.7 (3)C21—C22—C23—C180.9 (3)
C6—C9—C10—O4177.82 (17)C1—P—C24—C296.32 (15)
O3—C10—O4—C113.4 (3)C18—P—C24—C29126.35 (13)
C9—C10—O4—C11175.3 (2)C12—P—C24—C29118.58 (13)
C6—C2—C3—C4179.13 (14)C1—P—C24—C25171.07 (12)
C1—C2—C3—C40.77 (17)C18—P—C24—C2551.04 (14)
C2—C3—C4—C50.58 (18)C12—P—C24—C2564.03 (14)
C3—C4—C5—C10.13 (18)C29—C24—C25—C261.7 (2)
C2—C1—C5—C40.35 (17)P—C24—C25—C26179.07 (13)
P—C1—C5—C4178.97 (11)C24—C25—C26—C270.3 (3)
C1—P—C12—C13155.03 (13)C25—C26—C27—C281.0 (3)
C24—P—C12—C1328.37 (15)C26—C27—C28—C290.8 (3)
C18—P—C12—C1387.15 (14)C27—C28—C29—C240.6 (3)
C1—P—C12—C1728.48 (14)C25—C24—C29—C281.8 (2)
C24—P—C12—C17155.15 (13)P—C24—C29—C28179.26 (13)
(IIIb) dimethyl (E)-1-[2-(triphenylphosphoranylidene)cyclopentadien-1-yl]ethylenedicarboxylate top
Crystal data top
C29H25O4PDx = 1.287 Mg m3
Mr = 468.46Melting point: 507 K
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 8862 reflections
a = 14.8041 (9) Åθ = 2.8–22.3°
b = 18.0337 (12) ŵ = 0.15 mm1
c = 18.1151 (12) ÅT = 293 K
V = 4836.2 (5) Å3Plate, orange
Z = 80.30 × 0.25 × 0.10 mm
F(000) = 1968
Data collection top
Bruker SMART CCD area-detector
diffractometer
4261 independent reflections
Radiation source: fine-focus sealed tube3428 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.054
ϕ and ω scansθmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
h = 1717
Tmin = 0.856, Tmax = 0.985k = 2121
65646 measured reflectionsl = 2121
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: difference Fourier map
wR(F2) = 0.106All H-atom parameters refined
S = 1.06 w = 1/[σ2(Fo2) + (0.0568P)2 + 1.0912P]
where P = (Fo2 + 2Fc2)/3
4261 reflections(Δ/σ)max = 0.005
407 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C29H25O4PV = 4836.2 (5) Å3
Mr = 468.46Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 14.8041 (9) ŵ = 0.15 mm1
b = 18.0337 (12) ÅT = 293 K
c = 18.1151 (12) Å0.30 × 0.25 × 0.10 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
4261 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
3428 reflections with I > 2σ(I)
Tmin = 0.856, Tmax = 0.985Rint = 0.054
65646 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.106All H-atom parameters refined
S = 1.06Δρmax = 0.37 e Å3
4261 reflectionsΔρmin = 0.24 e Å3
407 parameters
Special details top

Experimental. Routine 1H and 13C NMR spectra were obtained on a Jeol JNMGX 270 MHz s pectrometer in CDCl3 at 25 ° C with TMS as internal standard unless otherwise stated. The 31P NMR spectra were recorded under the same conditions on a Varian Unity 300 MHz instrument with 85% orthophosphoric acid as external standard. The lamp used for the UV irradiation experiments was a commercially available 300 W sunlamp. UV/Visible spectra were obtained in 1 cm quartz cells on a Hewlett Packard spectrophotometer. IR spectra (KBr) were recorded on a Mattson Instruments spectrophotometer. Elemental analyses and mass spectra were carried out at UCD. The reactions were carried out under a N2 atmosphere dried by passing it through anhydrous calcium chloride. All commercially available chemicals were used without further purification unless specified. The liquid acetylene dicarboxylates (Aldrich) were stored under N2 and refrigerated. Cyclopentadiene was prepared from technical dicyclopentadiene and used immediately (Furnis et al., 1978). Solvents were dried according to standard procedures (Armerego & Perrin, 1988).

The phosphorane 3a (1.0 g, 2.14 mmol) was dissolved in dichloromethane (40 ml) in a 50 ml Pyrex round bottomed flask, and sealed under nitrogen with parafilm. The flask was placed 15 cm from the UV source (300 W lamp) and irradiated for 96 h. The wine coloured solution was evaporated and the brown-orange solid was recrystallized with dichloromethane/ethanol in a darkened flask to give yellow crystals. Yield = 0.9 g, (90%). Mpt. = 234 − 235 ° C. 1H NMR (Varian Unity 300 MHz): 7.72–7.45 (m, 15 H, aryl), 6.29, (m, 4H, cyclopentadienyl/vinyl), 3.61 (s, 3H, methyl), 3.05 (s, 3H, methyl) p.p.m.. 31P NMR: 12.7 p.p.m.. Anal. Calcd. (Found) for C29H25O4P: C, 74.35 (74.30): H, 5.38 (5.34). Mass spectrum: m/z 468 (M+), 409 (M+ –CO2Me). νmax (KBr): 2950, 2945, 2840, 1725, 1595, 1480, 1455, 1435, 1415, 1395, 1335, 1295, 1250, 1215, 1170, 1120, 1110, 1070, 1040, 1020 cm −1. λmax (logε, CH2Cl2): 260 (4.21), 407 (3.55) nm.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
P0.93819 (3)0.20465 (2)0.40917 (3)0.03082 (14)
C10.94262 (11)0.29998 (9)0.42185 (10)0.0343 (4)
C20.95622 (12)0.35872 (10)0.36950 (10)0.0355 (4)
C60.97066 (12)0.35688 (10)0.28957 (10)0.0405 (4)
C71.04337 (13)0.30729 (11)0.26002 (11)0.0443 (5)
O11.10442 (10)0.28353 (10)0.29588 (8)0.0642 (5)
O21.03266 (10)0.29254 (10)0.18816 (8)0.0629 (5)
C81.1008 (2)0.2453 (2)0.15505 (17)0.0793 (9)
H8A1.116 (2)0.200 (2)0.1887 (19)0.122 (13)*
H8B1.155 (2)0.2744 (17)0.1500 (16)0.095 (10)*
H8C1.077 (2)0.2279 (19)0.110 (2)0.118 (12)*
C90.92983 (14)0.40344 (12)0.24300 (13)0.0505 (5)
H90.9494 (14)0.4065 (12)0.1950 (12)0.053 (6)*
C100.85494 (16)0.45368 (13)0.26283 (13)0.0579 (6)
O30.85650 (14)0.51968 (10)0.25590 (15)0.1087 (8)
O40.78320 (10)0.41689 (8)0.28617 (9)0.0614 (4)
C110.7053 (3)0.4606 (2)0.3066 (3)0.0936 (11)
H11A0.722 (3)0.493 (3)0.344 (3)0.18 (2)*
H11B0.658 (3)0.428 (2)0.322 (2)0.133 (15)*
H11C0.685 (3)0.484 (2)0.267 (2)0.151 (19)*
C30.95517 (13)0.42445 (11)0.40994 (12)0.0441 (5)
H30.9648 (14)0.4729 (12)0.3895 (11)0.055 (6)*
C40.94314 (13)0.40891 (11)0.48433 (12)0.0424 (5)
H40.9426 (13)0.4439 (12)0.5233 (11)0.051 (6)*
C50.93455 (12)0.33335 (11)0.49232 (11)0.0386 (4)
H50.9242 (13)0.3084 (11)0.5367 (11)0.044 (5)*
C120.84927 (12)0.16382 (10)0.46552 (10)0.0343 (4)
C130.77179 (13)0.13407 (11)0.43428 (12)0.0426 (5)
H130.7677 (13)0.1320 (11)0.3823 (12)0.048 (6)*
C140.70244 (15)0.10773 (13)0.47869 (14)0.0552 (6)
H140.6497 (17)0.0876 (13)0.4533 (13)0.069 (7)*
C150.70922 (16)0.11159 (13)0.55383 (14)0.0568 (6)
H150.6588 (16)0.0965 (13)0.5846 (12)0.066 (7)*
C160.78605 (17)0.14004 (12)0.58557 (13)0.0544 (6)
H160.7936 (15)0.1425 (12)0.6362 (13)0.060 (7)*
C170.85685 (15)0.16493 (11)0.54238 (11)0.0444 (5)
H170.9121 (14)0.1833 (11)0.5636 (11)0.044 (5)*
C181.04078 (11)0.15908 (10)0.43861 (10)0.0341 (4)
C191.04462 (14)0.08235 (12)0.44735 (13)0.0515 (5)
H190.9895 (16)0.0504 (12)0.4371 (12)0.064 (6)*
C201.12390 (16)0.05007 (14)0.47114 (15)0.0642 (7)
H201.1252 (17)0.0029 (16)0.4742 (14)0.081 (8)*
C211.19785 (15)0.09250 (15)0.48749 (14)0.0600 (6)
H211.2519 (19)0.0726 (15)0.5059 (14)0.080 (8)*
C221.19423 (14)0.16816 (14)0.47917 (13)0.0537 (6)
H221.2448 (16)0.1991 (12)0.4915 (12)0.063 (7)*
C231.11579 (13)0.20141 (12)0.45429 (11)0.0421 (5)
H231.1108 (14)0.2538 (13)0.4477 (12)0.055 (6)*
C240.91303 (12)0.18013 (10)0.31510 (10)0.0343 (4)
C250.83974 (13)0.21415 (11)0.28089 (11)0.0422 (5)
H250.8072 (13)0.2524 (11)0.3046 (10)0.040 (5)*
C260.81128 (15)0.19011 (13)0.21218 (12)0.0521 (5)
H260.7609 (16)0.2131 (12)0.1901 (12)0.056 (6)*
C270.85673 (17)0.13395 (14)0.17707 (12)0.0591 (6)
H270.8351 (15)0.1149 (12)0.1305 (13)0.064 (7)*
C280.93143 (17)0.10274 (14)0.20929 (13)0.0600 (6)
H280.9630 (17)0.0656 (14)0.1852 (14)0.077 (8)*
C290.96005 (14)0.12492 (12)0.27833 (11)0.0464 (5)
H291.0114 (15)0.1019 (12)0.3008 (11)0.049 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P0.0293 (2)0.0290 (2)0.0342 (3)0.00132 (18)0.00077 (18)0.00017 (19)
C10.0342 (9)0.0307 (9)0.0380 (10)0.0024 (7)0.0017 (8)0.0011 (7)
C20.0319 (9)0.0326 (10)0.0419 (10)0.0027 (7)0.0010 (8)0.0040 (8)
C60.0370 (10)0.0412 (11)0.0433 (11)0.0078 (8)0.0015 (8)0.0073 (9)
C70.0372 (10)0.0559 (12)0.0400 (11)0.0051 (9)0.0035 (9)0.0082 (9)
O10.0526 (9)0.0916 (12)0.0483 (9)0.0211 (8)0.0022 (7)0.0014 (8)
O20.0508 (9)0.0978 (13)0.0403 (8)0.0139 (8)0.0039 (7)0.0030 (8)
C80.0576 (16)0.126 (3)0.0541 (16)0.0178 (18)0.0123 (13)0.0137 (18)
C90.0506 (12)0.0544 (13)0.0466 (12)0.0032 (10)0.0020 (10)0.0139 (10)
C100.0574 (13)0.0485 (13)0.0679 (15)0.0007 (11)0.0146 (11)0.0161 (11)
O30.0878 (14)0.0511 (11)0.187 (2)0.0051 (10)0.0036 (14)0.0371 (14)
O40.0521 (9)0.0515 (9)0.0806 (11)0.0049 (7)0.0002 (8)0.0013 (8)
C110.068 (2)0.084 (2)0.129 (3)0.0208 (18)0.008 (2)0.009 (2)
C30.0450 (11)0.0321 (10)0.0552 (12)0.0046 (8)0.0004 (9)0.0036 (9)
C40.0423 (11)0.0355 (10)0.0494 (12)0.0047 (8)0.0022 (9)0.0095 (9)
C50.0405 (11)0.0368 (10)0.0386 (10)0.0009 (8)0.0032 (8)0.0024 (9)
C120.0337 (9)0.0277 (9)0.0416 (10)0.0021 (7)0.0040 (8)0.0015 (8)
C130.0381 (11)0.0398 (11)0.0501 (12)0.0034 (8)0.0007 (9)0.0031 (9)
C140.0373 (11)0.0532 (14)0.0751 (16)0.0073 (10)0.0013 (11)0.0098 (12)
C150.0470 (13)0.0500 (13)0.0734 (16)0.0015 (10)0.0222 (12)0.0141 (12)
C160.0698 (15)0.0489 (13)0.0445 (13)0.0035 (11)0.0155 (11)0.0091 (10)
C170.0500 (12)0.0405 (11)0.0426 (11)0.0032 (9)0.0001 (9)0.0032 (9)
C180.0309 (9)0.0333 (10)0.0380 (10)0.0026 (7)0.0012 (7)0.0028 (8)
C190.0404 (11)0.0377 (11)0.0765 (16)0.0010 (9)0.0009 (10)0.0088 (10)
C200.0513 (14)0.0448 (14)0.0966 (19)0.0108 (11)0.0051 (12)0.0246 (13)
C210.0359 (11)0.0704 (17)0.0738 (16)0.0118 (11)0.0001 (11)0.0212 (13)
C220.0347 (11)0.0649 (15)0.0615 (14)0.0034 (11)0.0036 (10)0.0027 (12)
C230.0365 (10)0.0404 (11)0.0494 (12)0.0010 (9)0.0006 (9)0.0026 (9)
C240.0343 (9)0.0350 (9)0.0335 (9)0.0019 (8)0.0033 (7)0.0001 (8)
C250.0403 (10)0.0450 (12)0.0412 (11)0.0028 (9)0.0014 (9)0.0014 (9)
C260.0496 (12)0.0656 (15)0.0411 (12)0.0034 (11)0.0070 (10)0.0086 (10)
C270.0700 (15)0.0717 (16)0.0356 (11)0.0080 (13)0.0018 (11)0.0067 (11)
C280.0714 (16)0.0615 (15)0.0470 (13)0.0067 (13)0.0082 (12)0.0170 (11)
C290.0462 (11)0.0491 (12)0.0440 (11)0.0076 (10)0.0035 (9)0.0055 (9)
Geometric parameters (Å, º) top
P—C11.7357 (18)C13—C141.388 (3)
P—C241.7995 (18)C13—H130.94 (2)
P—C181.8074 (17)C14—C151.367 (3)
P—C121.8213 (18)C14—H140.98 (2)
C1—C51.416 (3)C15—C161.374 (3)
C1—C21.436 (2)C15—H150.97 (2)
C2—C31.393 (3)C16—C171.383 (3)
C2—C61.464 (3)C16—H160.93 (2)
C6—C91.335 (3)C17—H170.96 (2)
C6—C71.498 (3)C18—C231.377 (3)
C7—O11.193 (2)C18—C191.394 (3)
C7—O21.338 (2)C19—C201.379 (3)
O2—C81.450 (3)C19—H191.02 (2)
C8—H8A1.05 (4)C20—C211.368 (4)
C8—H8B0.96 (3)C20—H200.96 (3)
C8—H8C0.95 (4)C21—C221.374 (3)
C9—C101.476 (3)C21—H210.94 (3)
C9—H90.92 (2)C22—C231.382 (3)
C10—O31.197 (3)C22—H220.96 (2)
C10—O41.322 (3)C23—H230.95 (2)
O4—C111.445 (3)C24—C291.385 (3)
C11—H11A0.94 (5)C24—C251.392 (3)
C11—H11B0.95 (4)C25—C261.384 (3)
C11—H11C0.89 (4)C25—H250.94 (2)
C3—C41.388 (3)C26—C271.372 (3)
C3—H30.96 (2)C26—H260.94 (2)
C4—C51.376 (3)C27—C281.371 (3)
C4—H40.95 (2)C27—H270.97 (2)
C5—H50.93 (2)C28—C291.380 (3)
C12—C131.387 (3)C28—H280.93 (3)
C12—C171.397 (3)C29—H290.96 (2)
C1—P—C24112.12 (9)C12—C13—H13118.4 (12)
C1—P—C18112.30 (8)C14—C13—H13121.1 (12)
C24—P—C18109.98 (8)C15—C14—C13120.4 (2)
C1—P—C12110.71 (8)C15—C14—H14123.1 (14)
C24—P—C12106.37 (8)C13—C14—H14116.5 (14)
C18—P—C12104.96 (8)C14—C15—C16119.8 (2)
C5—C1—C2107.08 (16)C14—C15—H15120.1 (14)
C5—C1—P122.47 (14)C16—C15—H15120.1 (14)
C2—C1—P130.43 (14)C15—C16—C17120.8 (2)
C3—C2—C1106.18 (16)C15—C16—H16122.2 (14)
C3—C2—C6122.75 (17)C17—C16—H16116.9 (14)
C1—C2—C6131.06 (17)C16—C17—C12119.9 (2)
C9—C6—C2123.00 (19)C16—C17—H17122.0 (12)
C9—C6—C7118.35 (18)C12—C17—H17118.2 (12)
C2—C6—C7118.15 (16)C23—C18—C19119.60 (17)
O1—C7—O2123.24 (19)C23—C18—P119.11 (14)
O1—C7—C6124.36 (19)C19—C18—P121.27 (14)
O2—C7—C6112.41 (16)C20—C19—C18119.3 (2)
C7—O2—C8115.90 (19)C20—C19—H19120.1 (13)
O2—C8—H8A111.6 (19)C18—C19—H19120.6 (13)
O2—C8—H8B107.1 (19)C21—C20—C19120.8 (2)
H8A—C8—H8B108 (3)C21—C20—H20122.0 (15)
O2—C8—H8C107 (2)C19—C20—H20117.2 (16)
H8A—C8—H8C109 (3)C20—C21—C22120.0 (2)
H8B—C8—H8C114 (3)C20—C21—H21123.1 (17)
C6—C9—C10124.9 (2)C22—C21—H21116.9 (17)
C6—C9—H9119.6 (14)C21—C22—C23120.0 (2)
C10—C9—H9115.5 (13)C21—C22—H22121.4 (14)
O3—C10—O4123.2 (2)C23—C22—H22118.6 (14)
O3—C10—C9124.8 (2)C18—C23—C22120.3 (2)
O4—C10—C9111.91 (19)C18—C23—H23117.4 (13)
C10—O4—C11116.7 (2)C22—C23—H23122.3 (13)
O4—C11—H11A108 (3)C29—C24—C25119.63 (18)
O4—C11—H11B109 (2)C29—C24—P121.87 (15)
H11A—C11—H11B112 (4)C25—C24—P118.33 (14)
O4—C11—H11C108 (3)C26—C25—C24120.0 (2)
H11A—C11—H11C113 (4)C26—C25—H25118.9 (12)
H11B—C11—H11C106 (3)C24—C25—H25121.1 (12)
C4—C3—C2109.89 (18)C27—C26—C25119.9 (2)
C4—C3—H3125.3 (13)C27—C26—H26121.1 (13)
C2—C3—H3124.8 (13)C25—C26—H26119.0 (13)
C5—C4—C3108.29 (18)C28—C27—C26120.1 (2)
C5—C4—H4125.5 (13)C28—C27—H27119.6 (14)
C3—C4—H4126.2 (13)C26—C27—H27120.3 (14)
C4—C5—C1108.55 (18)C27—C28—C29121.0 (2)
C4—C5—H5125.6 (12)C27—C28—H28120.3 (16)
C1—C5—H5125.8 (12)C29—C28—H28118.8 (16)
C13—C12—C17118.59 (17)C28—C29—C24119.3 (2)
C13—C12—P121.70 (15)C28—C29—H29120.3 (12)
C17—C12—P119.66 (14)C24—C29—H29120.4 (12)
C12—C13—C14120.5 (2)
C24—P—C1—C5160.85 (14)C18—P—C12—C1754.89 (16)
C18—P—C1—C574.72 (17)C17—C12—C13—C141.6 (3)
C12—P—C1—C542.24 (17)P—C12—C13—C14175.73 (16)
C24—P—C1—C220.8 (2)C12—C13—C14—C150.8 (3)
C18—P—C1—C2103.67 (17)C13—C14—C15—C161.6 (3)
C12—P—C1—C2139.37 (16)C14—C15—C16—C170.0 (3)
C5—C1—C2—C30.4 (2)C15—C16—C17—C122.4 (3)
P—C1—C2—C3178.99 (15)C13—C12—C17—C163.2 (3)
C5—C1—C2—C6178.47 (18)P—C12—C17—C16174.24 (16)
P—C1—C2—C60.1 (3)C1—P—C18—C2311.74 (18)
C3—C2—C6—C944.6 (3)C24—P—C18—C23113.86 (16)
C1—C2—C6—C9136.7 (2)C12—P—C18—C23132.09 (15)
C3—C2—C6—C7127.19 (19)C1—P—C18—C19166.74 (16)
C1—C2—C6—C751.5 (3)C24—P—C18—C1967.66 (18)
C9—C6—C7—O1152.7 (2)C12—P—C18—C1946.39 (19)
C2—C6—C7—O119.5 (3)C23—C18—C19—C200.4 (3)
C9—C6—C7—O227.1 (3)P—C18—C19—C20178.90 (19)
C2—C6—C7—O2160.75 (17)C18—C19—C20—C211.2 (4)
O1—C7—O2—C80.2 (3)C19—C20—C21—C221.0 (4)
C6—C7—O2—C8179.5 (2)C20—C21—C22—C230.0 (4)
C2—C6—C9—C1010.6 (3)C19—C18—C23—C220.6 (3)
C7—C6—C9—C10177.63 (19)P—C18—C23—C22177.94 (16)
C6—C9—C10—O3122.0 (3)C21—C22—C23—C180.8 (3)
C6—C9—C10—O461.1 (3)C1—P—C24—C29135.13 (16)
O3—C10—O4—C112.5 (4)C18—P—C24—C299.43 (19)
C9—C10—O4—C11179.5 (3)C12—P—C24—C29103.72 (17)
C1—C2—C3—C41.0 (2)C1—P—C24—C2549.75 (17)
C6—C2—C3—C4178.03 (17)C18—P—C24—C25175.46 (14)
C2—C3—C4—C51.2 (2)C12—P—C24—C2571.40 (16)
C3—C4—C5—C10.9 (2)C29—C24—C25—C263.4 (3)
C2—C1—C5—C40.3 (2)P—C24—C25—C26171.82 (16)
P—C1—C5—C4178.42 (14)C24—C25—C26—C271.6 (3)
C1—P—C12—C13110.80 (16)C25—C26—C27—C281.4 (4)
C24—P—C12—C1311.25 (17)C26—C27—C28—C292.6 (4)
C18—P—C12—C13127.80 (16)C27—C28—C29—C240.7 (4)
C1—P—C12—C1766.50 (17)C25—C24—C29—C282.3 (3)
C24—P—C12—C17171.45 (15)P—C24—C29—C28172.80 (17)

Experimental details

(IIIa)(IIIb)
Crystal data
Chemical formulaC29H25O4PC29H25O4P
Mr468.46468.46
Crystal system, space groupMonoclinic, P21/nOrthorhombic, Pbca
Temperature (K)293293
a, b, c (Å)13.7622 (15), 11.8849 (13), 15.8788 (17)14.8041 (9), 18.0337 (12), 18.1151 (12)
α, β, γ (°)90, 107.914 (2), 9090, 90, 90
V3)2471.3 (5)4836.2 (5)
Z48
Radiation typeMo KαMo Kα
µ (mm1)0.140.15
Crystal size (mm)0.50 × 0.40 × 0.360.30 × 0.25 × 0.10
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Bruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2002)
Multi-scan
(SADABS; Sheldrick, 2002)
Tmin, Tmax0.877, 0.9500.856, 0.985
No. of measured, independent and
observed [I > 2σ(I)] reflections
43496, 6129, 5100 65646, 4261, 3428
Rint0.0270.054
(sin θ/λ)max1)0.6670.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.127, 1.05 0.043, 0.106, 1.06
No. of reflections61294261
No. of parameters407407
H-atom treatmentAll H-atom parameters refinedAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.41, 0.160.37, 0.24

Computer programs: SMART (Bruker, 2001), SMART, SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 2002) and ORTEPIII (Burnett & Johnson, 1996), SHELXTL.

Comparative geometrical data for (IIIa), (IIIb) and (I) top
Bond Lengths (Å)Z-isomer (3a)E-isomer (3 b)Ramirez ylide (1)
P-C11.7412 (14)1.7357 (18)1.718 (2)
C1-C21.4496 (19)1.436 (2)1.430 (3)
C1-C51.411 (2)1.393 (3)1.392 (4)
C2-C31.409 (2)1.388 (3)1.401 (4)
C3-C41.389 (2)1.376 (3)1.376 (4)
C4-C51.411 (2)1.416 (3)1.419 (3)
P1-C121.8173 (15)1.8213 (18)-
P1-C181.8045 (14)1.8074 (17)-
P1-C241.8044 (15)1.7995 (18)-
C2-C61.438 (2)1.464 (3)-
C6-C71.513 (2)1.498 (3)-
C6-C91.344 (2)1.335 (3)-
C9-C101.456 (2)1.476 (3)-
Bond Angles (°)Z-isomer (3a)E-isomer (3 b)Ramirez ylide
C2-C1-P131.86 (11)130.43 (14)125.3 (2)
C5-C1-P120.84 (11)122.47 (14)125.3 (2)
C5-C1-C2107.29 (12)107.08 (16)107.4 (2)
C1-C2-C3105.89 (13)106.18 (16)106.8 (2)
C2-C3-C4109.65 (14)109.89 (18)108.9 (2)
C2-C6-C7114.76 (13)118.15 (16)-
C6-C9-C10124.08 (15)124.9 (2)-
 

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