Magnetic nonequivalence in asymmetric phosphorus compounds

L. FRANKEL, J. CARGIOLI, H. KLAPPER, AND R. DANIELSON

Pl?ysical Cl~ernistryDepartmerzt, Clzemical Research Laboratory, Edgewood Arsenal, Maryland, 21010 Received April 17, 1969 The nuclear magnetic resonance (n.m.r.) spectra of seven compounds of the type (CHB)P(O)(SCH,SR)(OR') have been examined as a function of solvent. The resonance pattern of the methylene protons, SCH,S, is strongly solvent dependent. In solvents of low dielectric constant, the methylene protons are magnetically nonequivalent and are observed as the AB part of an ABX spin system, where X is the phosphorus atom. In high dielectric constant medium (DMSO d6) only a well-resolved doublet is obtained indicating magnetic equivalence. When R' = CH(CH3),, nonequivalent methyl groups which show analogous solvent effects are observed. Eight compounds of the type (CH3)P,(O)(OCH(CH3),)(X) have been studied. The chemical shift between the magnetically nonequivalent isopropyl methyl groups does not correlate with any simple property of X.
Canadian Journal of Chemistry. 47, 3167 (1969)

Introduction Several i1.m.r. studies have been reported on the effect of asymmetric carbon atoms in causing magnetic nonequivalence (1). An asymmetric phosphorus atom may also cause magnetic nonequivalence in nearby methylene protons (2, 3) and methyl groups (4-6). The origin of the magnetic nonequivalence is strictly due to symmetry effects (7) which may be further augmented by the effect of conformational preference. For all previously reported systems rapid intramolecular rotation occurs. The experimental parameters observed are averages over all conformers (7).

gating conformer preference, because individual conformer frequencies are generally expected to be both temperature and solvent dependent to a much greater degree than JK,i coupling constants (8)We wish to report our findings on the organophosphorus coinpounds in Tables I and V. Comparisons are made with the factors (solvent, temperature, and substituent effects) that influence the spectra of asymmetric carbon atoms.

Experimental

Spectra were obtained on a Varian HA-100 spectrometer. When required, supplementary spectra were obtained on a Varian A-60 spectrometer. All the compounds [I = CiXi(~A,i - VB,~) reported are liquids. Their spectra were obtained in a 10% by volun~esolution which contained less than 5 % by J~= CiXiJK,i volume of TMS. The compounds in Tables I and V were supplied by where Xi is the mole fraction of a particular conMr. Ray Irino (Organic Chemistry Department of this former and the sum is over all conformers. JKYi laboratory) or obtained from commercial sources. Genand vXyi are the coupling constants and frequen- eral characterizations of those compounds not commercies of a particular conformer. It has been cially available will be reported at a later date. The n.m.r. previously pointed out that chemical shift differ- spectra were in consonance with the proposed structures.

ences are usually of questionable use for investiTABLE I Compounds of the type (CH3)P(0)(SCH2SR)(ORf)have been investigated No. R

R'
Cyclopentyl CH(CH3)z CH(CH3)z CH(CH3)z CH(CH3)z Cyclopentyl CH(CH3)z

Results and Discussion The SCH,S methylene protons of the compounds in Table I form the AB part of an ABX spin system where X is the phosphorus atom. A typical spectrum is shown in Fig. 1 (the second peak from the right contains two overlapping peaks). The spectra were analyzed as previously described (3). The coupling constants JAx and JBx may be of like or unlike sign. A comparison of the 100 and 60 Mc.p.s. spectra definitively shows that the coupling constants have the same relative sign (3). The magnitude of the coupling constants

CANADIAN JOURNAL O F CHEMISTRY. VOL. 47, 1969

FIG.1. The 100 Mc.p.s. spectra of the SCHzS ~nethyleneprotons of co~npound 3 (Table I) in benzene.
TABLE I1 Nuclear magnetic resonance data for (CH3)P(0)(SCH2SCH3)(OCH(CH3)2) as a function of solvent No.
1 2 3 4

Solvent Cyclohexane dl eel, Benzene d6 C,CL

E*

lJax Jnxlc.p.s.
24.5 24.9 24.3 24.4 24.5 24.1 23.8 23.1 24.7 22.7 23.0 22.48

J,xc.P.s. 13.5 13.4 13.3 13.4 12.9 13.1 12.6 12.6 13.0 12.0 12.1 11.2

8CH, p.p.m:i
0.147 0.135 0.216 0.140 0.108 0.097 0.071 0.065 0.066 0.02 0.059 <0.01

&H,

p.p.m.!c 0.074 0.072 0.147 0.068 0.063 0.045 0.048 0.039 0.041 0.031 0.025 0.029

2.05 2.24 2.28 2.30 5.05 7.0 21.4 33.1 36.7 37.5 48.9

6 7 8 9 10 11 12 13

CC~,D CD3I Neat Acetone d6 CD-OD D ~ d, F CD3NOZ DMSO d6

NOTE:The following parameters show only a 50.2 c.p.s. variation with solvent J P C H = 3 15.9 c.P.s., JAB= 13.2 c.p.s., Jcl,,cA,.,l= Jce3(o).n= 6.3 c.P.~. *Dielectric constant of protonated solvents. tThe chemical shift between nonequivalent methylene protons. $The chemical shift between nonequivalent methyl groups. Assumed to be twice JAx.

JHx (Tables I1 and 111), 9 < JHx < 14 c.p.s., is within the expected range (3, 9). Assignment of different signs would lead to one unusually large value for JHx. Since the errors in JAx and JBx can be large while the errors in their sum is small, only the latter quantity is considered. From a detailed analysis of the AB part of the ABX spectrum, one obtains three manifestations

of the nonequivaleilce of the methyleile protons. These parameters are listed in Tables I1 and IV. They are: ( I ) proton coupling between nonequivalent methylene protons, JAB; (2) a chemical shift difference between nonequivalent methylene protons, 6,,,; (3) heteronuclear proton phosphorus coupling which in general is different for different Protolls, JH(A),x # JH(B) ,P

FRANKEL ET AL.: MAGNETIC NONEQUlVALENCE

TABLE I11 Summary of variable temperature results in CC13D TC

IJAx

+ JBxl c.p.s.

JAx c.p.s.

~CH,

P.P.m.

~ C H *

P.P.~.

*As the temperature is lowered, JAB increases from 13.2 c.p.s. (57 "C) to 13.6 c.p.s. (-62 "C) and Jnx increases from 11. 3 c.p.s. (57 "C) to 11.7 c.p.s. (-62 O C ) . ?As the temperature is lowered, J A B increases from 13.3 c.p.s. (56 O C ) to 13. 6 c.p.s. (-62"C), and JDx increases from 11.0 c.p.s. (56 'C) to 11. 6 c.p.s. (-62 "C).

TABLE IV Summary of results for compounds in Table I Compound*

1

Solvent CCIA ca, CsDs CCI, CsDs CCI,

JPCII~

C.P.S.

JAB

C.P.S. 13.1

[JAx

JBX~

C.P.S.

8 c ~ ~ P . P . n l . 8cH,p.p.nl. 0.133

16.2

24.4

c s ~ i Neat DMSO 7
eel,

C,D, DMSO

15.8 15.9 15.7 16.0 16.2 16.0

13.3
$ 13.3 13.1 $

?-

23.4 22.4 21.8s 24.5 23.2 22.2s

0.132 <0.02 <0.01 0.080 0.128 <0.01

0.074 0.134 0.034

*See Table I for identification of compounds. ?The spectrum is not sufficiently resolved to permit calculations. SThe methylene protons are equivalent in DMSO. Assumed to be twice JAx.

The i1.m.r. data for the SCH2S methylene protons of compound 2 (Table I) as a function of solvent are summarized in Table 11. Figure 2 clearly shows that JJAx JBxJ and SCH2 depend on common factors. In DMSO d6 the methylene protons appear as a well-resolved doublet with a line width at half height which is identical to that of the PCH3 methyl group (0.5 c.p.s.). Previously it had been suggested that a primary prerequisite for magnetic nonequivalence to be observable in

an asymmetric phosphorus compound was that one of the substituents be a benzene ring (4). Our data as well as that of Rowsell (5) clearly show this need not be the case. The R' group of compound 2 also contains a magnetically nonequivalent set of methyl groups. The spectrum of these methyl groups is two doublets separated by an internal chemical shift SCy3, The data for the methyl groups are included in Table 11.

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(I) by taking a more cognizant picture of the microscopic dielectric medium which may be primarily governed by solvent anisotropy. While it is not readily possible to separate micro-macro dielectric effects, attention is called to the fact that the above views are not necessarily divergent (12, 13).

VS. lJAX JDX( of the SCH2S FIG. 2. A plot of methylene protons of 2 ( ~ ~ 3 ) ~ ( 0 ) ( ~ ~ ~ 2 (CH;)~) in various solvents. The experimental points are numbered by solvents according to Table 11.

~ ~ ~ 3 ) ( ~ ~ ~ -

Assuming JKSi is constant for the same compound in different solvents, the extent of conformer preference of the SCH,S protons may be with solexamined. The small variation of JpcH, vent supports this assumption. As the temperature is increased the degree of conformer preference, determined by the relative values of Xi (eq. [I]), decreases. The results of a variable temperature study summarized in Table I11 suggest that the smaller values of JJAX + JDX( are associated with reduced conformer preference. Intervening groups between the asymmetric phosphorus atom and the nonequivalent protons do not allow a simple representation of the conformers. The solvents in Table I1 are arranged with regard to increasing dielectric constant. IJAx + JBxI shows decreasing conformer preference with increasing dielectric constant. Similar solvent effects have been observed in symmetry restricted phosphorus (3) and carbon analogues (10-12). The degree of conformer preference follows an inverse dependence with the dielectric constant of the solvent in agreement with the predictions of an electrostatic model (12). Previous explanations of similar results have generally considered two major factors, (I) solvent dielectric constant effects and (2) solvent anisotropy effects. The latter can be included within

FIG. 3. The chemical shift of the methylene protons SCH2S vs. the chemical shift of the isopropyl methyl groups of (CH3)P(0)(SCH2SCH3)(OCH(CH3)2) in various solvents. The experimental polnts are numbered by solvent according to Table 11.

The spectra of the isopropyl methyl groups are relatively insensitive to temperature (Table 111). Figure 3 shows that the degree of magnetic nonequivalence of FCH,and 6,,, are related. Apparently the medium dielectric constant is a primary factor in determining the magnitude of the magnetic nonequivalence. Some exceptions to the trends discussed are noted. Both 6,,, and 6,,, are unusually large in benzene as is typical of aromatic solvents (11,12). In Fig. 2, the values for methanol clearly deviate from the general trend. A reasonable explanation for this is that hydrogen bonding between the phosphoryl group and/or the lone pair sulfur electrons and methanol is responsible.

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3171

An interesting feature of the data in Table I1 is that in solvents of low dielectric constant ScH, > 6,,, while in high dielectric media, the reverse may hold. The results for the other compounds in Table I, summarized in Table IV, show similar solvent effects. In benzene the methyl protons on R of compounds 6 and 7 (Table I) are observed as a sharp doublet due to coupling with the methine proton. No evidence for long range magnetic nonequivalence is observed. Roberts et al. (1) have reported nonequivalent methyl groups seven bonds removed from an asymmetric carbon atom. An attempt was made to see if the degree of magnetic nonequivalence of the isopropyl methyl groups could be correlated to the nature of one of the substituents at the asymmetric center (11).
TABLE V A comparison of the degree of magnetic nonequivalence of the isopropyl methyl groups of (CH3)P(O)(OCH(CH3)~)(X) in benzene X
&lr,

Compounds of the following type were examined, (CH3)P(0)(OCH(CH3),)(X), in benzene and the results summarized in Table V. Although S,,, shows large variations as X is varied, there is no obvious effect such as steric hindrance or electronegativity that can account for the observed variation of 6,,,. The pseudo asymmetric compound listed in Table V, (CH,)P(O)(OCH(CH,),),, is the methyl analogue of a compound reported by Finegold (14) which has been discussed by Waugh and Cotton (15). The compounds (H)P(O)(OCH(CH,),), (6,,, = 0.029, p.p.m.) and (pheny1)P(O)(OCH(CH,),), (6$,, = 0.107 p.p.m.) also show magnetic nonequivalent methyl groups.
1. G. M. WHITESIDES, D. HOLTZ,and J. D. ROBERTS. J. Am. Chern. Soc. 86, 2628 (1964). 111. J. Phys. Chern. 70, 2249 (1966). 2. T. H. SIDDALL 3. L. S. FRANKEL, H. KLAPPER,and J. CARGIOLI. J. Phys. Chern. 73, 91 (1969). 4. T. H. SIDDALL I11 and C. A. PROHASKA. J. Am. Chern. Soc. 84,2502, 3467 (1962). 5. D. G. ROWSELL.J. Mol. Spectry. 23, 32 (1967). 6. R. KEAT and W. SIM. Chern. Cornrnun. 4,191 (1968). 7. J. A. POPLE. Mo1. Phys. 1, 1 (1958). 8. H. S. GUTOWSKY, G. G. BELFORD, and P. E. MCMAHON. J. Chern. Phys. 36, 3353 (1962). 9. J. W. EMSLEY, J. FEENEY, and L. H. SUTCLIFFE. High resolution nuclear magnetic resonance. Vol. 2. The Pergarnon Press, Ltd., London. 1966. Table
12-62.

P.P.~.

10. R. V. MOEN and W. H. MUELLER.J. Org. Chem. 31, 1971 (1966). 11. G. M. WHITESIDES, J. J. GROCKI, D. HOLTZ,H. STEINBERG. and J. D. ROBERTS.J. Am. Chem. Soc.
*Range of results reported i n Tables I1 and IV. ?For X = F, fi, is too small to be measured accurate~y.~ $No evidence of magnetic nonequivalence is observed for X = OH or 0CH3.

12. E.'I. S N & E R ~ ' J . Am. Chern. Soc. 85, 2624 (1963). 13. S. SELTZER and S. G. MYLONAKIS. J. Phys. Chem. 72, 754 (1968). 14. H. FINEGOLD. J. Am. Chern. Soc. 82, 2641 (1960). 15. J. S. WAUGH and F. A. COTTON. J. Phys. Chem. 65, 562 (1961).