J . Am. Chem. SOC.1991, 113, 27-32
21
Multiphase Characterization of Phosphorus Sulfides by Multidimensional and MAS-31P N M R Spectroscopy. Molecular Transformations and Exchange Pathways at High Temperaturest T. Bjorholm*,t and H. J. Jakobsen*,s Contribution from the Cheminova AIS, P . 0. Box 9, DK-7620 Lemvig, Denmark, and Department of Chemistry, University of Aarhus, DK-8000 Aarhus C,Denmark. Received May 29, 1990
Abstract: High-temperature 1D and 2D e--hange 3’P-NMR spectra of melts of pure and well-defined phosphorus sulfides show that, e.g., p-P4S5 or mixtures of P4S3and sulfur transform into mixtures of at least eight different P4Sn(n,,= 3-7) species which are identified and quantified. Transformations and exchange pathways between the different P4S,species in the melts are revealed by the 2D exchange 3iP-NMRspectra at 225-250 O C . Furthermore, the exchange correlations observed from these spectra yield unambiguous assignments of the unknown or earlier incorrectly assigned 31Pchemical shifts for p-P&,, and a new P4S6isomer (ff-P4s6).These assignments are extremely valuable for a correct interpretation of p-P4S5, a-P4SS, the complex solid-state magic angle spinning (MAS)-NMR spectra of phosphorus sulfides. Two polymorphs for both @-PIS5 and @-P4s6(the predominant species in the @-P4S5 melt and isolated here for the first time) have been isolated and characterized by high-speed 31PMAS-NMR spectroscopy. Molecular distortions, caused by crystal packing and not easily detected by XRD, are observed for all four polymorphs. These distortions cause nonequivalence between phosphorus atoms which are equivalent for the free molecules. Thereby otherwise unobservable isotropic ’J(P,P)’shave been determined from solid-state NMR spectroscopy.
Phosphorus and sulfur form a fascinating series of P,S, (3 I n I 10) compounds which have been studied extensively by different spectroscopic techniques over the years. Some of these phosphorus sulfides are produced in thousands of tons per year from high-temperature melts of the elements and used in manufacturing of insecticides, lubricating oil, additives, plasticizers, flame retardants, etc. Depending on the employed molar ratios of phosphorus and sulfur, very complex mixtures of phosphorus sulfides are obtained. Because these mixtures are difficult to analyze, especially in the molten state, the exact PIS, compositions for the melts are only partly understood. Solution-state 31P N M R spectra have been reported for P4S3,I a-P4S4?p-P4S4,2a-P4S5.3 @-P4S5,4 P4S7.395P4S2 (unstable), P4S9.7 and P4SlJ(molecular structures shown in Figure I). The spectral assignment of the 31Presonances for P4S3,a-P4S4,/3-P4S4,P4S9, and P4Slo is straightforward and unambiguous from the molecular symmetries, relative intensities, and one-bond 31P-3iPscalar couplings. From the data of these compounds it is obvious that no simple relationship exists between the 3iPchemical shifts and the various phosphorus moieties in the different P4S, species. Consequently, the assignments of 31PN M R spectra of already well-known (e.g., C Y - P ~ @-P4S5,4 S ~ , ~ and P4ST3)and potentially new P4S, species are often restricted to indirect evidences and assumptions based on comparison with the data for the unambiguously assigned species. Infrared and Raman investigationss-” have shown that the phosphorus sulfides transform during melting into a series of PIS, species. Although the compositions of these melts are usually very complex and only the predominant compounds have been identified by these techniques, the existence of p*P4s6 in some of the melts is indisputable. However, @-P4s6has not been isolated until now, and no 3 i PN M R data have been reported so far for this species. Complementary to the early solution-state 31PN M R studies there has recently been a renewed interest in a series of P4S, compounds from a solid-state 3’P magic angle spinning (MAS) point of view. Detailed reports have been given for the 3 1 P MAS-NMR spectra for P4S3,I2-l4 P4S7,5J2J3 P4S9,I2and P4S10.12Because of the high spectral complexity attributable to crystallographically nonequivalent phosphorus atoms, crystalpacking distortions, and large ” P chemical shift anisotropies ‘Presented at the “31st ENC”, Asilomar, CA, April 1990. ‘Cheminova A/S. *University of Aarhus.
0002-7863/91/ I5 13-27$02.50/0
(CSA’s), these spectra can yield valuable information pertinent to the solid state of the compounds. However, an unambiguous assignment of the many resonances in these highly complex spectra is a prerequisite for a correct interpretation of the data. In the present work we have studied the I D and 2D exchange (NOESY) 31PNMR spectra of high-temperature melts for &P4S5 and for two mixtures of P4S3and sulfur. The result of these investigations in a clear-cut way identifies the transformation products and establishes exchange pathways between the different P4S, species generated in the melts. Furthermore, the correlation of the 3 i Pchemical shifts for the P4S, species obtained from the exchange-correlated spectra permits unambiguous assignments and the of the 3 i PN M R spectra for @-P4s6,P-P4Ss, and a-P4S5 identification of a hitherto unknown P4s6 isomer (~vP4S6,Figure 1). We also report the 31P MAS-NMR spectra of two polymorphic forms of /3-P4S6$isolated for the first time as a solid during this investigation, and of two polymorphic forms of /3-P4S5,one well-known4and the other isolated during the course of this study.
(1) Heckmann, G.;Fluck, E. Z . Naturforsch. 1971, 268, 982-986. (2) Griffin, A. M.; Minshall, P. C.; Sheldrick, G. M. J . Chem. Soc., Chem. Commun. 1976, 809-810. (3) Thamm, R.; Heckmann, G.;Fluck, E. Phosphorus Sulfur 1981, 1 1 , 273-278. (4) Griffin, A. M.; Sheldrick, G. M . Acta Crystallogr. Sect. B 1975, 31, 2738-2740. (5) Bjorholm, T. Chem. Phys. Lett. 1988, 143, 259-262. (6) Barieux, J.-J.; DCmarcq, M. C. J . Chem. SOC.,Chem. Commun. 1982, 176-177. (7) Andrew, E. R.; Vennart, W.; Bonnard, G.; Croiset, R. M.; Demarcq, M. C.; Mathieu, E. Chem. Phys. Lett. 1976, 43, 317-320. (8) Gardner, M. J . Chem. SOC.,Dalton Trans. 1973, 691-696. (9) Bues, W.; Somer, M.; Brockner, W. Z . Anorg. Allg. Chem. 1981,476, 153-158. (IO) Bues, W.; Somer, M.; Brockner, W. Z . Naturforsch. 1981, 360, 842-845. ( I I ) Somer, M.; Bues, W.; Brockner, W. Z . Naturforsch. 1983, 380, 163-1 66. (12) Eckert, H.; Liang, C. S.; Stucky, G. D. J . Phys. Chem. 1989, 93, 452-457. (13) Harris, R. K.; Wilkes, P. J.; Wood, P. T.; Woollins, J . D. J , Chem. Soc., Dalton. Trans. 1989, 809-8 13. (14) Bjorholm, T.; Jakobsen, H. J. J . Magn. Reson. 1989, 84, 204-21 I . (15) Jakobsen, H. J.; Langer, V.; Daugaard, P. J . Magn. Reson. 1988, 76, 162-168; US. Patent, Patent Number 4,739,270, April 19, 1988. (16) Hazell, R. G. Department of Chemistry, University of Aarhus, DK-8000 Aarhus C, Denmark, to be published.
0 1991 American Chemical Society
28
Bjorholm and Jakobsen
J . Am. Chem. SOC.,Vol. 113, No. 1, 1991
-
bl
I P'S,Il.21
m
I qS,lapicall
PI X
m:
X
Y
Y I¶
P-PiSi
Lone-poir
lone-pair
E : a-P,5,
5
tone-pair
Y ' a-P,S,
5
5
PI : P - P 1 S 5 m : p-PLSB m:P'sl
a-P's,l21
h e - p a i r (one-poir
5 5
Lone-poir S
Figure 1. Molecular structures of the phosphorus sulfides discussed and
studied in this work. The numbering of the P atoms and of the P4S, species corresponds to that used throughout the text, figures, and tables.
Experimental Section Preparation of the Phosphorus Sulfides. P4S3 was purchased from Fluka and purified by recrystallization from CS2. a-P4S5and P4S7were prepared following the procedures outlined in the l i t e r a t ~ r e .p-P4S5 ~ was obtained by desulfurization of P4S7.9The hitherto nonisolated /3-P4S6was prepared from P4S7according to the following procedure. A suspension of P4S7 in CS2 was reacted under reflux with an equimolar quantity of (C6Hs)3P,added dropwise as a solution in CS2 during 30 min. After evaporation of the solvent, the material was recrystallized from CS2to yield yellow crystals of /3-P4S6. The crystals showed no well-defined melting point because of the molecular transformations and exchange processes observed at high temperatures (vide supra). The purity of /3-P4S6as well as for B-P4S5 was assessed by solution-state (CS,) 31P N M R spectroscopy. Several batches of both /3-P4S5and p-P4s6 were prepared. Whereas no impurities could be detected for the samples of /3-P4Ss,the optimum purity of /3-P4S6was approximately 90-92%, with /3-P4S5and P4S7 constituting unavoidable impurities by the method of preparation. Solution and High-Temperature "P-NMR Spectroscopy. Room-temperature solution-state and high-temperature molten-state NMR spectra were acquired on a Bruker AC 250 spectrometer by using a specially designed high-temperature (maximum 400 "C) water-cooled 5-mm probe selectively tuned to the 31Pfrequency of 101.3 MHz. The temperature stability was better than f 2 OC. The duration of the n/2 pulse was 5 p s , The molten-state spectra were recorded in an unlocked mode, and for the 1 D spectra a 2-ps pulse and a relaxation delay of 100 s were used to ensure full recovery of the magnetization. A temperature of ca. 200 OC was employed for the 1 D spectra since this gives optimum resolution (minimum line widths) for the spectra. The 2D 3'P exchange spectra were acquired by using the pulse sequence NOESYPH from the Bruker software. The relaxation delay was 2-4 s. To suppress correlation effects from scalar couplings the mixing time T, (generally about 100-200 ms) was randomly varied by 10-20%. The temperature for the 2D experiments was increased to ca. 250 OC in order to obtain appropriate exchange rates for the molecular transformations during 7,. To avoid air contact in the molten state, the solid samples were degassed and sealed under vacuum in heavy-wall N M R tubes. "P chemical shifts for the CS2 solutions are referenced to an external sample of 85% H!P04. Chemical shifts for the melts are referenced via the high-frequency singlet observed for P4S7 and taken as 1 1 1 .I ppm relative to 85% H3P04. Solid-state "P MAS-NMR Spectroscopy. 31PMAS-NMR spectra were obtained on a Varian XL-300 spectrometer (7.1 T) at 121.42 MHz by using a home-built high-speed spinning CP/MAS probe.ls Cylindrical 7 mm 0.d. Si3N4rotors with a sample volume of 220 pL and spinning
b 100
2LO
220
200
180
160
1LO
120
80
60
PPm
Figure 2. The 101.3 MHz ,IP N M R spectra of melts of (a) /3-P4S5and (b) of a 1:l molar mixture of P4S3and sulfur (P4S4,,,) recorded at 196 O C after the samples have been held at 250 "C for 30 min in the probe. The high-frequency singlet for P4S7( I 1 1.1 ppm) has been used as reference. The numbers in parentheses indicate the individual 3'P resonances of the P4S, species and correspond to the labeling of the phosphorus nuclei shown in Figure 1. The four multiplets indicated by asterisks (*) in spectrum (a) correspond to the ABMX spin system of the novel P4S6isomer, ff-P4S6 (see text). To visualize all minor P4S, constituents in spectrum (b), the full intensity of the inner lines of the 1:3:3:1 quartet for P4S3 (apical) is not shown. Vertical and 7.5-ppm horizontal expansions of the three multiplets for p-P4S4 are shown as insets in spectrum (b).
speeds in the range from 4.0 to 9.5 kHz were employed. A pulse width of 3 ,us, corresponding to a 35O flip angle, and a relaxation delay of 20 s were used for all samples. The "P chemical shift scale was referenced to an external sample of 85% H 3 P 0 4 by substitution.
Results and Discussion High-Temperature Melts. Figure 2 a shows t h e 1D 31PNMR spectrum of p-P4S5recorded a t 196 OC after the sample has been heated to 250 "C in t h e probe for a b o u t 30 min. This spectrum clearly indicates that the p-P4S5melt disproportionates in a clean way t o a series of P4S, species. T h e corresponding spectra for the two mixtures of P4S3and sulfur with overall compositions P4S3,6 a n d P4S4,0,respectively, show a similar appearance albeit t h e mutual ratios of t h e P4S, compounds a r e different. T h e spectrum of t h e mixture with t h e overall composition of P4S4,0is shown in Figure 2b. A n unambiguous assignment of t h e 3 1 P1 D spectra, a n d thereby of t h e P4S, species in t h e melts, follows in a straightforward m a n n e r from comparison of t h e 31Presonances (multiplets) in Figure 2 with t h e solution-state d a t a in t h e lite r a t ~ r e l -and, ~ furthermore, from t h e 2 D exchange spectra (vide infra). T h e only exceptions for a direct comparison with t h e literature d a t a a r e t h e predominant species in t h e p-P4S5melt, shown t o be p-P4s6, a n d a new P4s6 isomer (vide infra). T h e assignment of t h e 3'P resonances t o t h e different PIS, species in t h e melts a r e indicated in Figure 2a, whereas their molar ratios (%), obtained by integration, a r e listed in T a b l e I. These percentages account exactly for the sulfur content of t h e melts. 31P chemical shifts and 31P-31Pcoupling constants for the P4S, species observed in t h e melts (196 "C) a r e summarized in T a b l e 11; for comparison their CS, solution-state d a t a a r e also given.
Table I. Compositions of P4S, Species (mol %) in Melts of p-P4S5 and P S I + Sulfur' at 196 "C
I . I4 g of P4S3+ 0.16 g of sulfur (P4S40). and 1.OO + 0.09 g of sulfur (p4s3.6). The 31Psolution-state (cs2) spectrum of the @P4S6 crystals
" Compositions: g of
.
J . Am. Chem. SOC.,Vol. 113, No. 1 , 1991 29
Phosphor us Sulfides
P4s3
obtained by partial desulfurization of P4S7 (see Experimental Section) gives an AMzX spin system which exactly matches the spectrum observed for the predominant species in the p-P4S5melt. There is no direct experimental evidence (e& from 2D exchange spectra) for the assignment of P3 and P4 for &P4S6. However, comparison of the two-bond 31P_31P coupling constants determined for p-P4Ss(45.0 Hz) and P4S7(0.9 Hz) with the related couplings for p-P4s6 (46.3 and 1 1 . I Hz) leads to the assignment of the P3 and P4 resonances for pmP4S6given in Table 11. The existence of p-P4s6 in the molten state of p-P4ss and of different P4s4 isomers has earlier been established by Bues et aL9,I0by using infrared and Raman spectroscopy. They showed that p-P4S5and the P4S4isomers decompose during melting into complex mixtures and p-P4s6 were of phosphorus sulfides of which P4S3, P4s7, identified. The similarity between the N M R spectra of the three melts studied here indicates that the transformation products may exist as reversible equilibria. The 2D 31PN M R exchange spectrum of the melt of /3-P4Ssat 250 OC (Figure 3) confirms this suggestion in that exchange networks for several of the P4S, species can be mapped out. It is evident from this spectrum that the disproportionation of @-P4S5involves the insertion of one and two exocyclic sulfur atoms with the formation of @-P4s6and P4S7,respectively, as revealed by cross-peaks for the following equilibrium in Scheme I. In a recent solid-state 31PMAS investigation on P4S75we have unambiguously (re)assigned the CS2solution-state 31Presonances for P4S7at 84.7 and 1 1 1.1 ppm to PI ,P2 and P3,P4, respectively. By using these diagonal peaks (singlets at 89.6 and 11 1. I ppm in the melt at 196 "C) as starting points, the assignment of the 31Presonances in p-P4s6 and p-P4s5given in Table 11are obtained. The intense cross-peak observed between P3 and P4 in pmP4S6 reflects exchange of the position for the terminal sulfur atom in this molecule (most likely intramolecular). By this interchange the chemical shift for PI and P2 is unaffected as the symmetry of the molecule is preserved.
*+
*-------
mIL(1,21
I
I
I
I
I
I
120
1
~
Il6O
I I I
1
I
I
1
2.40 200 160 120 80 40 PPm Figure 3. Phase-sensitive 2D exchange 3 1 PN M R spectrum of a melt of p-P4S5at 250 OC (after equilibration for about 30 min at this temperature) obtained by using a mixing time ',,, = 100 ms. The assignments, given along the diagonal, correspond to the formulas shown in Figure 1 with the individual "P nuclei indicated in parentheses. For comparison see the 1 D "P spectrum in Figure 2a. The signal indicated by an asterisk (*) is the fold-in for the basal doublet of P4S3. The connecting lines for the exchange equilibria p-P4ss s p-P4s6 Z= P4s7are drawn as examples. Scheme I
The 2D 31PN M R exchange spectrum of the melt with composition P4S4.0 (recorded at 225 OC and T , = 0.2 s, Figure 4) displays the same exchange networks as observed for the @-PISs melt. However, for this melt the concentration of p-P4S4 has increased to a level that allows transformation cross-peaks to be observed between PI,P3 in p-P4S4and the two separate PI and P3 resonances for a-P4SS.Unfortunately, the resonances for P1 ,P3 in p-P4s4and P4 in p-P4s6 partly overlap as seen in the Figure 4 2D exchange spectrum; however, on the expanded contour plot and a plot of the slice (at 205.3 ppm) through the diagonal peak for PI ,P3 in @-P4S4, shown in Figure 5, the correlation is easily recognized. In addition, further evidence for the transformation
Table 11. "P Chemical Shifts and alp-slp Coupling Constants' for p-P4S4,N - P ~ SN-P& ~, p-P4S5,p-P4s6, and P4S7in Solutionb and in Melts (196 "C)' ff-P4S5 N-PqS6 @p4s6 solution melt solutiond melt solution melt solution melt solution melt 6(P1) 124.9 136.9 54.9 65.7 129.8 142.3 178.2 184.8 84.7 89.2 91.7 103.6 57.9 59.3 129.8 142.3 178.2 184.8 84.7 89.2 W2) 115.8 114.9 80.1 87.2 55.7 61.0 111.1 111.1 6(P3) 127.0 129.8 b(P4) 233.8 237.4 133.5 132.3 80.1 87.2 198.9 206.7 111.1 111.1 J(PI,P2) -184.7' (-)189.3 152.9 158.2 J ( P 1,P3) 119.0 113.0 124.9 125.0 45.0 42.3 11.1 14.1 0.9 5.9 18.1 16.5 19.0 19.5 2.2 7.2 45.0 42.3 46.3 45.1 0.9 5.9 J(PI,P4) 11.1 14.1 0.9 5.9 J(P2,P3) 168.7 173.8 -285.4' (-)289.6 239.8 245.0 45.0 42.3 51.3 53.3 52.3 20.0 25.8 45.0 42.3 46.3 45.1 0.9 5.9 J(P2,P4) 50.5 J(P3,P4) 18.1 16.5 27.9 30.4 19.1 17.1 113.3 108.9 rms error 0.25 0.84 0.03 0.41 0.05 0.57 0.20 0.34 0.31 0.31 0.05 0.40 "All spectral parameters result from iterative computer fitting of the 3 1 Pline frequencies for the relevant four-spin systems corresponding to the structures shown in Figure I ; chemical shifts are in ppm and coupling constants in Hz; rms errors are given in the last row of the table. bSaturated solutions using CS2 as solvent with chemical shifts relative to 85% H3P04. CChemicalshifts for the melt are referenced via the high-frequency singlet (taken as 1 1 1 .I ppm relative to 85% H3P04)for P4S7observed in the spectrum. dFrom dissolution of the cooled melt in CS2. eThe negative sign for J(PI,P2) and J(P2,P3) follows from the analysis of the ABMX spin system observed at low field (2.3 T; "P at 40 MHz).) Note that the spectrum has been rcassigned compared to the results in ref 3 (see text). solutiond 207.5 85.7 207.5 174.7 168.7
melt 205.0 97.0 205.0 185.8 173.8
30 J. Am. Chem. SOC.,Vol. 113, No. 1. 1991
Bjorholm and Jakobsen
- 40
- PPm - 80 - 120. - 160
1
-
- 200 - 240 1
1
240
1
1
1
200
1
160
1
1
120
1
1
1
40 ppm
80
Figure 4. Phase-sensitive 2D exchange 3'P N M R spectrum of a melt of the 1:l molar mixture of P4S3 and sulfur (P4S40)at 225 "C (after equilibration for about 30 min at 250 "C) obtained by using a mixing time T , = 200 ms. The assignments, given along the diagonal, correspond to the formulas shown in Figure 1 with the individual 31Pnuclei indicated in parentheses. Some assignments and chemical exchange equilibria already shown in Figure 3 are not indicated here. The signal indicated by an asterisk (*) is the fold-in for the basal doublet of P4S3. The connecting lines for the exchange processes p-P4S4 s a-P4SS s a-P4S6are drawn as examples.
I
I
I
I
1
,
I
O
I
I
2LO 200 160 120 80 LO PPm Figure 5. Expansion of the contour plot for the 2D exchange )IP N M R spectrum in Figure 4. A plot of the slice through the diagonal for P1,P3 at 205.3 ppm is shown above the expanded contour plot in @-P4S4(llI) (see text).
p-P4S4 + a-P4S5 is obtained (Figure 4) from observations of cross-peaks between the P4 (and P2) resonances in p-P4S4and a-P4S5. Although the assignment of the A2MX spin system for p-P4S4is unambiguous (based on the Jpp's;see also Figure 2b), the 2D exchange spectrum produces no information about the mutual assignment of the resonances for PI and P3 in a-P4S5. However, assignment of the multiplet at 129.8 ppm to P3 and the multiplet at 136.9 ppm to PI for a-P4S5 brings the spin-spin couplings 2J(PI ,P4) and 2J(P2,P4) close to the corresponding values observed in p-P4S4.2 Analogously to the (intramolecular) interconversion observed for p-P4S6 a similar rearrangement is seen for a-P4S5by virtue of the cross-peak between the resonances at 129.8 (P3) and 136.9
Scheme I1 Q
ppm (Pl). The presence of less than 1% p-P4S4in the @-P4S5melt strongly indicates that the symmetric exchange process for a-P4S5 is dominated by an intramolecular mechanism. For all 2D exchange spectra cross-peak intensities are observed between resonances for a-P4S5and those of an unknown ABMX spin system. Owing to the lack of symmetry and bearing in mind that all exchange processes observed in the 2D exchange spectra involve formation/breaking (rearrangement) of double bonds between sulfur and phosphorus (P=S), this species is most probably a novel P4s6 isomer (wP4S6) derived from a-P4s5by insertion of an exocyclic sulfur at P2 or P4. In addition to the equilibrium depicted in Scheme I the 2D exchange spectrum of the P4& melt reveals an additional equilibrium based on the p-P4S4cage (Scheme 11). The only known phosphorus sulfide with the a-P4S4cage is a-P4S4itself. However, weak cross-peak intensities are observed in Figure 4 between a-P4S4and an unknown P4S, species. The very low concentration of this new compound in the melts (
