Article pubs.acs.org/Organometallics
Novel Spirooxaphosphirane Complexes Rainer Streubel,* Eva Schneider, and Gregor Schnakenburg Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Straße 1, 53121 Bonn, Germany S Supporting Information *
ABSTRACT: Reaction of a transient Li/Cl phosphinidenoid pentacarbonyltungsten complex 3 (R = C5Me5) with 3oxetanone, dihydro-3(2H)-furanone, and dihydro-4H-pyran-4one led to the novel spirooxaphosphirane complexes 5, 7a,b, and 9a,b having an additional oxygen atom in the ring system, while δ-valerolactone furnished selectively the P,C-cage complex 10. All complexes have been characterized by heteronuclear NMR and mass spectrometry and by single-crystal Xray analysis in the case of 7a and 9a.
S
Attempts to synthesize derivatives with a (second) oxygen atom in a position α to the spiro carbon center were not successful.
piroalkanes such as spiropentanes (I) have been intensively studied,1 and although spiroheterocycles are present in a large number of natural products2 and show physical properties of particular interest,3 the area of phosphorus-containing spiroheterocycles is deeply underdeveloped. Furthermore, the research has been focused on phosphorus−carbon ring systems4 such as the phospha-spiropentanes II−IV (Scheme 1). Whereas most derivatives of II5,6 and III7 were bound to a
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RESULTS AND DISCUSSION Deprotonation of complex 114 and chlorine/lithium exchange in 2,15 using lithium diisopropylamide (1) or tert-butyllithium (2) in the presence of 12-crown-4 at low temperature, led to the transient Li/Cl phosphinidenoid complex 3, which was reacted in situ with the ketone derivatives 4, 6, and 8 to yield the spirooxaphosphirane tungsten complexes 5, 7a,b and 9a,b (Scheme 2). Although the reaction of complex 3 with 4 proceeded quite cleanly to complex 5 (content about 85% according to 31P{1H} NMR integration), the workup, i.e. extraction at low temperature, proved to be very difficult and even very cautious handling let to partial decomposition in solution and formation of a product displaying a very broad signal at about 115.4 (h1/2 = 65 Hz; 75%) in the 31P{1H} NMR spectrum. Therefore, a reliable NMR data set for 5 could not be obtained. In contrast to the case for 5, isomers a,b were formed in the case of 7 and 9 (7a,b, 35:65; 9a,b, 7:93; determined via integration of the 31 1 P{ H} NMR spectra); the major product was always isomer b, displaying a more high-field-shifted resonance. In both cases, the two isomers could not be separated and thus have been purified and characterized only as mixtures. It should be noted that complexes 7a,b displayed a higher stability in solution than 5 but also decomposed slowly at ambient temperature (∼12 h) to give products with very broad signals at about 127.2 (h1/2 = 112 Hz; 50%) and 118.3 ppm (h1/2 = 341 Hz; 42%) in the 31 1 P{ H} NMR spectra. The origin of the isomerism in complexes 7a,b is obvious as the spiro center is stereogenic. In complexes 9a,b the isomerism may be due to the different conformations of the oxygencontaining six-membered-ring system (chair or boat, etc.) in
Scheme 1. Spiropentane (I), Phospha-Spiropentane Derivatives II−IV and Phospha-Spiroheterocycles Va
a
R denotes an organic substituent, the dashed line in V indicates various ring sizes, and E indicates a heteroatom other than phosphorus.
transition-metal center,8 the only known derivative of IV9 (all tert-butyl substituted) was obtained in a nonligated fashion. Theoretical investigations on monocyclic oxaphosphirane derivatives concerning ring strain (23.2 kcal/mol for the parent system and 22.0 kcal/mol for a trimethyloxaphosphirane complex)10 together with recent experimental studies on acidinduced ring opening11 of monocyclic oxaphosphirane complexes have demonstrated that they are new valuable building blocks. On the basis of the convenient methodology for oxaphosphirane complexes, developed recently,12 interest increased to investigate spiroheterocycles of type V13 as new ligand systems having various ring sizes and various heteroatoms E in different positions. Here, the synthesis of novel spirooxaphosphirane complexes possessing an oxygen atom in various positions of the spiro ring system (E = O) is reported; all complexes display a thermal stability lower than that of their all-carbon spiro derivatives. © 2012 American Chemical Society
Received: February 24, 2012 Published: June 26, 2012 4707
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Article
Scheme 2. Synthesis of the Spirooxaphosphirane Complexes 5, 7a,b, and 9a,b
which the oxygen atom may point toward or away from the pentacarbonyltungsten fragment. The other option, an exocyclic P−C atropisomerism, which was recently discovered13 in a related problem for the CH(SiMe3)2 substituent, can be ruled out, as such an isomerism was never detected before in one of the many structures of P-Cp*-substituted phosphorus heterocyclic complexes reported so far. The molecular structures of complexes 7b and 9b were unambigously confirmed by single-crystal X-ray analysis; for selected data see Figures 1 and 2. In general, complexes 5, 7a,b, and 9a,b showed phosphorus resonances between 35 and 58 ppm, similar to the values of monocyclic oxaphosphirane
Figure 2. Molecular structure of complex 9b. Selected bond lengths (Å) and angles (deg): W−P = 2.4971(12), C1−O1 = 1.484(4), C1−P = 1.798(4), C4−O2 = 1.423(5), O2−C3 = 1.429(5); O1−P−C1 = 50.54(15), C1−O1−P = 69.3(2), O1−C1−P = 60.17(18), C4−O2− C3 = 110.7(3).
complexes. Within this series of spirooxaphosphirane complexes the trend became apparent that, with increasing ring sizes, the resonance was shifted to lower field (Table 1), and the relative position of the oxygen (in the larger ring) had just a small effect, if any. Complexes 5, 7a,b and 9a,b all showed very similar 1J(W,P) coupling constant magnitudes.15 The 13C{1H} NMR spectra revealed that the resonances of the spiro center carbon nuclei (Cspiro) are shifted toward lower field with decreasing ring size (5-ring > 6-ring). The molecular structures of 7b and 9b were confirmed by single-crystal X-ray crystallography. The structure of complex 7b shows a disorder in the furanone part (77.6:22.4). The oxygen atom in the envelope conformation (7b) is pointing toward (main) or away (minor) from the pentacarbonyltungsten fragment (Figure 1); in the case of 9b a chair conformation was found (Figure 2). Both structures show acute and nearly
Figure 1. Molecular structure of complex 7b in the crystal (77.6% main orientation of the furanone ring (solid line) and 22.4% (dashed line), disorder between O2 and C4; hydrogen atoms are omitted for clarity). Selected bond lengths (Å) and angles (deg): W−P = 2.4723(12), P−O1 = 1.671(3), C1−O1 = 1.482(5), P−C1 = 1.792(5), C2−O2 = 1.389(7), C4−O2 = 1.420(12); O1−P−C1 = 50.52(18), C1−O1−P = 69.0(2), O1−C1−P = 60.5(2), C2−C1−C5 = 104.9(4), C2−O2−C4 = 101.4(6). 4708
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Table 1. 31P{1H}, 1H, and 31C{1H} NMR Data (CDCl3) of Complexes 5, 7a,b, and 9a,b
a
Article
EXPERIMENTAL SECTION
All reactions were carried out under an inert gas atmosphere using purified and dried argon and standard Schlenk techniques. Solvents were dried over sodium wire/benzophenone and distilled under argon. NMR data were recorded on a Bruker DMX 300 spectrometer at 25 °C using C6D6 as solvent and internal standard; chemical shifts in ppm relative to tetramethylsilane (1H, 300.13 MHz; 13C, 75.5 MHz), and 85% H3PO4 (31P, 121.5 MHz). IR spectra were recorded on a Nicolet 80 FT-IR spectrometer using KBr plates. Mass spectra were recorded on a MAT 95 XL Finnigan (EI, 70 eV, 184W) spectrometer; selected data are given. Elemental analyses were performed by using an Elementar VarioEL instrument. General Procedure for the Synthesis of Complexes 5, 7a,b, and 9a,b. To a freshly prepared solution of complex 3 (266 mg, 0.50 mmol) in THF (6 mL) was added 5 equiv of the ketone derivative 4, 6, or 8 (0.18 mg/0.15 mL of 3-oxetanone, 0.22 mg/0.19 mL of dihydro-3(2H)-furanone, 0.25 mg/0.23 mL of dihydro-4H-pyran-4one), and the reaction was warmed to 0 °C. The solvents were removed in vacuo (∼10−2 mbar) and the products were extracted with a 1:1 mixture of Et2O and n-pentane and purified by column chromatography (Al2 O 3 , −20 °C, petroleum ether). During chromatography the percentage of diethyl ether was increased from an initial ratio of 95:5 to finally pure diethyl ether. Complexes 7a,b and 9a,b were isolated as mixtures (white solids). 5: 31P{1H} NMR δ 35.2 (sSat, 1JW,P = 297.1 Hz); MS m/z (EI) 562 [(M)•+, 4], 490 [((CO)5PCp* − CO)•+, 3], 406 [((CO)2WCp*)•+, 6], 378 [((CO)WPCp*)•+, 3], 350 [(WPCp*)•+, 135 [(Cp*)•+, 100], 119 [(Cp* − Me − H)•+, 44], 105 [(Cp* − 2Me)•+, 25], 91 [(Cp* − 2Me − CH2)•+, 12]. 7a,b: yield of the mixture 109 mg (0.19 mmol, 38%); mp 76 °C; analytical data obtained from a 35:65 mixture of 7a,b; assignment to the isomers a and b is based solely on relative intensities; 1H NMR δ 0.61 (d, 3JP,C = 12.2 Hz, 3H, Cp* C1−CH3, isomer a), 0.76 (d, 3JP,C = 11.8 Hz, 3H, Cp* C1−CH3, isomer b), 1.52 (s, 3H, Cp* CH3), 1.57 (s, 6H, Cp* CH3), 1.56−1.65 (m, 18H, Cp* CH3), 1.83−1.87 (m, 1H, CH2, isomer a), 1.87 (s, 3H, Cp* CH3), 1.91 (s, 6H, Cp* CH3), 1.92− 1.98 (m, 2H, CH2, isomer b), 2.02−2.16 (m, 2H, CH2, isomer b), 2.28−2.44 (m, 1H, CH2, isomer a), 3.51−3.68 (m, 4H, CH2), 3.70− 3.80 (m, 2H, CH2), 3.88−3.97 (m, 2H, O−CH2, isomer b), 4.02−4.12 (m, 2H, O−CH2, isomer a), 4.29−4.38 (m, 2H, O−CH2, isomer b); 13 C{1H} NMR δ 11.2 (d, JP,C = 2.9 Hz, Cp* CH3), 11.3 (d, JP,C = 2.9 Hz, Cp* CH3), 11.8 (d, JP,C = 1.3 Hz, Cp* CH3), 12.0 (d, JP,C = 2.4 Hz, Cp* CH3), 12.1 (d, JP,C = 2.6 Hz, Cp* CH3), 12.5 (d, JP,C = 1.6 Hz, Cp* CH3), 16.4 (d, 1JP,C = 6.5 Hz, Cp* C1−CH3, isomer a), 16.8 (d, 1JP,C = 5.8 Hz, Cp* C1−CH3, isomer b), 33.9 (s, CH2, isomer b), 38.4 (d, 2JP,C = 6.5 Hz, CH2, isomer a), 65.0 (d, 1JP,C = 11.3 Hz, Cp* C1), 65.2 (d, 1JP,C = 11.6 Hz, Cp* C1), 65.9 (d, JP,C = 7.8 Hz, OCH2), 68.2 (d, JP,C = 4.3 Hz, OCH2), 70.9 (d, JP,C = 4.3 Hz, OCH2), 71.3 (d, 1 JP,C = 20.4 Hz, Cspiro), 75.4 (d, JP,C = 11.4 Hz, OCH2), 72.3 (d, 1JP,C = 20.4 Hz, Cspiro), 134.2 (d, JP,C = 8.4 Hz, Cp*), 134.2 (d, JP,C = 8.4 Hz, Cp*), 139.9 (d, JP,C = 3.2 Hz, Cp*), 140.3 (d, JP,C = 3.2 Hz, Cp*), 142.5 (d, JP,C = 7.1 Hz, Cp*), 145.0 (d, JP,C = 7.8 Hz, Cp*), 145.1 (d, JP,C = 7.8 Hz, Cp*), 195.6 (d, 2JP,C = 8.1 Hz, cis-CO), 195.7 (d, 2JP,C = 8.3 Hz, cis-CO), 196.4 (d, 2JP,C = 35.2 Hz, trans-CO), 196.6 (d, 2JP,C = 35.2 Hz, trans-CO); 31P{1H} NMR δ 38.3 (sSat, 1JW,P = 296.7 Hz, isomer b), 43.8 (sSat, 1JW,P = 298.4 Hz, isomer a); IR (KBr, selected data) ν̃ (cm−1) 2074 (s, shoulder, ν(CO)), 1966 (m, ν(CO)), 1917(s, ν(CO)); MS m/z (EI) 576 [(M)•+, 46], 548 [(M − CO)•+, 11], 492 [(M − 3CO)•+, 38], 490 [((CO)5WPCp*)•+, 44], 436 [(M − 5CO)•+, 5], 406 [((CO)3WPCp*)•+, 100], 378 [((CO)2WPCp*)•+, 31], 350 [((CO)WPCp*)•+, 15], 166 [(PCp*)•+, 5], 135 [(Cp*)•+, 96], 119 [(Cp* − Me − H)•+, 44], 105 [(Cp* − 2Me)•+, 25], 91 [(Cp* − 2Me − CH2)•+, 16]. Anal. Calcd for C19H21O7PW (576.18): C, 39.61; H, 3.67. Found: C, 39.76; H, 3.99, 9a,b: yield of the mixture 145 mg (0.25 mmol, 48%); mp 104 °C; analytical data obtained from a 7:93 mixture of 9a,b; the assignment to the isomers a and b is solely based on relative intensities. 9a: 31P{1H} NMR δ 57.3 (sSat, 1JW,P = 294.5 Hz).
Not determined.
identical endocyclic angles at phosphorus (50.5°). The C−O bond distances in the oxaphosphirane unit in 7b (1.482(5) Å) and 9b (1.484(4) Å) are somewhat longer than those in the spiro-ring parts of 7b and 9b (∼139−142 Å). In a first study attempts were made to react δ-valerolactone with the transient complex 3 (prepared via both routes), but here only the selective formation of the P,C-cage complex 1016 was observed (Scheme 3), and no spectroscopic evidence for Scheme 3. Attempted Reaction of Phosphinidenoid Complex 3 with δ-Valerolactone To Give 10
the formation of the targeted spirooxaphosphirane complex was obtained. This lack of reactivity might be possible to overcome if a phosphinidenoid complex with higher thermal stability could be employed.
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CONCLUSIONS Novel spirooxaphosphirane complexes possessing an oxygen atom in the spiro ring system were synthesized using a Li/Cl phosphinidenoid complex and cyclic ketones. Whereas in the case of the [5,3] combination in complexes 7a,b the origin of the isomerism is obvious, as the spiro carbon center is stereogenic, in complexes 9a,b it may be due to different conformations of the oxygen-containing six-membered-ring system. In contrast to spirooxaphosphirane complexes possessing an all-carbon cycle, all complexes of the present study are thermally much less stable in solution. The decomposition tendency inversely correlates with the ring size ([4,3] > [5,3] > [6,3]), and products thus formed display very broad 31P{1H} NMR signals but could not be further characterized. First attempts to use a lactone derivative failed, thus revealing a reactivity that is too low and, hence, self-reaction of the phosphinidenoid complex prevailed. 4709
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9b: 1H NMR δ 0.78 (d, 3JP,C = 10.6 Hz, 3H, Cp* C1−CH3), 1.59 (s, 3H, Cp* CH3), 1.64 (s, 3H, Cp* CH3), 1.73−1.78 (m, 2H, CH2), 1.92 (s, 3H, Cp* CH3), 2.00−2.16 (m, 2H, CH2), 3.60−3.88 (m, 4H, OCH2); 13C{1H} NMR δ 11.4 (d, JP,C = 3.2 Hz, Cp* CH3), 11.9 (d, JP,C = 1.3 Hz, Cp* CH3), 12.2 (d, JP,C = 2.6 Hz, Cp* CH3), 12.6 (d, JP,C = 1.0 Hz, Cp* CH3), 18.6 (d, 1JP,C = 6.5 Hz, Cp* C1−CH3), 33.2 (s, CH2), 38.3 (d, 2JP,C = 6.5 Hz, CH2), 65.3 (d, 1JP,C = 14.5 Hz, Cp* C1), 66.5 (d, 3JP,C = 1.3 Hz, OCH2), 66.7 (d, 3JP,C = 5.2 Hz, OCH2), 67.3 (d, 1JP,C = 15.8 Hz, Cspiro), 134.9 (d, JP,C = 9.7 Hz, Cp*), 141.6 (d, JP,C = 3.2 Hz, Cp*), 141.9 (d, JP,C = 65 Hz, Cp*), 144.8 (d, JP,C = 8.1 Hz, Cp*), 195.9 (d, 2JP,C = 8.4 Hz, cis-CO); 31P{1H} NMR δ 47.2 (sSat, 1 JW,P = 297.7 Hz); IR (KBr, selected data) ν̃ (cm−1) 2074 (s, shoulder, ν(CO)), 1927 (s, ν(CO)), 1704 (m, ν(CO)); MS m/z (EI) 590 [(M)•+, 3], 562 [(M − CO)•+, 7], 534 [(M − 2CO)•+, 2], 506 [(M − 3CO)•+, 1], 450 [(M − 5CO)•+, 1], 406 [((CO)2WPCp*)•+, 10], 378 [((CO)WPCp*)•+, 3], 166 [(PCp*)•+, 4], 135 [(Cp*)•+, 100], 119 [(Cp* − Me − H)•+, 44], 105 [(Cp* − 2Me)•+, 25], 91 [(Cp* − 2Me − CH2)•+, 12]. Anal. Calcd for C20H23O7PW (590.21): C, 40.70; H, 3.93. Found: C, 41.84; H, 4.12. Crystal Data for 7b. Suitable single crystals of 7b were obtained from a concentrated n-pentane solution cooled to −20 °C. Data were collected with a Nonius KappaCCD diffractometer equipped with a low-temperature device at 100 K by using graphite-monochromated Mo Kα radiaton (λ = 0.710 73 Å). The structure was solved by Patterson methods (SHELXS-97)17a and refined by full-matrix least squares on F2 (SHELXL-97).17b Data are as follows: C19H21O7PW, Mr = 576, colorless, crystal dimensions 0.290 × 0.230 × 0.040 mm3, monoclinic, space group P21/c, Z = 4, a = 10.8467(6) Å, b = 14.8130(8) Å, c = 12.9188(7) Å, β = 96.470(2)°, V = 2062.47(19) Å3, Dexptl = 1.856 g cm−3, μ = 5.715 mm−1, T = 100(2) K, transmission factors (min/max) 0.2880/0.8036, analytical absorption correction based on the indexing of the crystal faces,15 2θmax= 59.0°, 4974 unique data, Rint = 0.0666, R1 (for I > 2σ(I)) = 0.0349, wR2 (for all data) = 0.0732, final R = 0.0537, goodness of fit 1.023, ΔF(max/min) = +1.627/−1.815 e Å−3. Crystal Data for 9b. Suitable single crystals of 9b were obtained from a concentrated n-pentane solution cooled to −20 °C. Data were collected with a Nonius KappaCCD diffractometer equipped with a low-temperature device at 123.2 K by using graphite-monochromated Mo Kα radiation (λ = 0.710 73 Å). The structure was solved by Patterson methods (SHELXS-97)17a and refined by full-matrix least squares on F2 (SHELXL-97).17b Data are as follows: C20H23O7PW, Mr = 590, colorless, crystal dimensions 0.160 × 0.120 × 0.050 mm3, monoclinic, space group P21/c, Z = 4, a = 9.7676(3) Å, b = 8.3207(3) Å, c = 27.1396(10) Å, β = 101.583(2)°, V = 2160.80(13) Å3, Dexptl = 1.814 g cm−3, μ = 5.458 mm−1, T = 123(2) K, transmission factors (min/max) 0.4755/0.7720, analytical absorption correction based on the indexing of the crystal faces,15 2θmax= 80°, 5090 unique data, Rint = 0.0570, R1 (for I > 2σ(I)) = 0.0321, wR2 (for all data) = 0.0616, final R = 0.0566, goodness of fit 0.937, ΔF(max/min) = +2.137/−1.645 e Å−3. Crystallographic data of 7b and 9b have been deposited at the Cambridge Crystallographic Data Centre under the numbers CCDC 868293 (7b) and CCDC 868294 (9b). These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
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ACKNOWLEDGMENTS We are grateful to the Deutsche Forschungsgemeinschaft (No. STR 411/29-1) and the COST action cm0802 “PhoSciNet” for financial support; G.S. is grateful to Prof. A.C. Filippou for support.
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REFERENCES
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ASSOCIATED CONTENT
S Supporting Information *
CIF files giving crystal data for 7b and 9b. This material is available free of charge via the Internet at http://pubs.acs.org.
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[email protected]. Fax: (+) 49-228-73-9616. Notes
The authors declare no competing financial interest. 4710
dx.doi.org/10.1021/om300152y | Organometallics 2012, 31, 4707−4710
