Journal of Molecular Structure 700 (2004) 312 www.elsevier.

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Low-temperature NMR spectra of uoride acetic acid hydrogen-bonded complexes in aprotic polar environment
Nikolai S. Golubeva, Peter M. Tolstoya,b, Sergei N. Smirnova, Gleb S. Denisova, Hans-Heinrich Limbachb,*
a

V.A. Fock Institute of Physics, St Petersburg University, Ulyanovskaja 1, Peterhof, Russian Federation b Institut fuer Chemie der Freien Universitaet Berlin, Takustrasse 3, D14195 Berlin, Germany Received 20 January 2004; revised 20 January 2004; accepted 21 January 2004

Abstract Using low-temperature NMR (1H, 19F) technique in the slow exchange regime, the solutions containing tetrabutylammonium (TBA) acetate and HF have been studied in an aprotic freon mixture, CDF3/CDF2Cl, exhibiting a dielectric permittivity, which increases strongly by lowering the temperature. Two different hydrogen bonded anionic clusters, a 1:1 cluster of the type AcOd2 H F21 d ([AcOHF]2) and a 2:1 cluster of the type AcOH F2 HOAc ([(AcOH)2F]2) have been detected in equilibrium with each other, both forming ion pairs with the TBA countercation. [AcOHF]2 exhibits an extremely strong hydrogen bond, with a proton shared between partially negatively charged oxygen and uorine atoms. The NMR chemical shifts and scalar spin spin coupling constants, 1 JFH; have been measured in the temperature range between 110 and 160 K, where separate NMR signals are observed for both species. In addition, H/D isotope effects on the 19 F NMR chemical shielding have been measured for both clusters. In contrast to the related complexes [(FH)nF]2 n 1 4 studied previously, the NMR parameters of [AcOHF]2 and of [(AcOH)2F]2 depend strongly on temperature. This effect is associated with the increasing polarity of the solvent with decreasing temperatures, established earlier, which displaces the proton from uorine to oxygen. As a motive power of this conversion, preferential solvation of the compact uoride ion as compared to acetate is proposed. q 2004 Elsevier B.V. All rights reserved.
Keywords: Low-temperature NMR; Hydrogen bond; Isotope effect; Acetic acid; Fluoride anion

1. Introduction Strong and short (low-barrier) hydrogen bonds in charged (anionic or cationic) complexes (clusters) have attracted recently the attention of many biochemists due to presumed role of these bonds in enzymic catalysis [1 11]. One of the main questions when invoking the concept of low-barrier hydrogen bonding to biochemical reactions is how these bonds are affected by the surrounding water molecules or other polar groups. In fact, the problem of how solvent polarity inuences the length, strength and symmetry of a short hydrogen bond in charged complex has discussed in the literature for a long time. Some
* Corresponding author. Tel.: 49-30-8385-5375; fax: 49-30-83855310. E-mail addresses: [email protected] (H.-H. Limbach), [email protected] (N.S. Golubev), [email protected]. de (P.M. Tolstoy). 0022-2860/$ - see front matter q 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.molstruc.2004.01.024

experimental and theoretical results are in favour of solvent assisted hydrogen bond weakening, lengthening and asymmetrization, which makes the participation of such bonds in enzymic processes doubtful [12]. On the other hand, in some recent studies [13 15] it was shown that hydrogen bonds in homoconjugated anions are strengthened and contracted by embedding into a polar medium. This nding is in agreement, in particular, with the increase of the scalar 2h JFHF spin coupling constant between uorine nuclei across the hydrogen bonds with increasing polarity of the solvent for the dihydrogen triuoride ion, which exhibits two coupled short hydrogen bonds of the type [F H F H F]2 [16,17]. A simple explanation of this effect was proposed, i.e. that the electrostatic repulsion between negatively charged uorine atoms is reduced by a medium of high dielectric constant 1 [15]. Taking in mind, that a solvent may act on H-bonds of different type in different ways, in this communication we

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describe the inuence of the solvent polarity on the NMR parameters of ionic clusters with strongly asymmetric hydrogen bonds, formed by hydrogen uoride with the acetate-anion, in ion pairs with the inert tetrabutylammonium (TBA) counter cation. As described in our previous papers [18 20], we took advantage of a very strong dependence of 1 of the low-freezing solvent CDF3/ CDF2Cl on temperature. According to Ref. [18], 1 of this mixture rises rapidly from about 25 to 45 when temperature is decreased from 170 to 100 K. This makes it possible to study the dependence of the NMR parameters as a function of 1 without changing the solvent. At temperatures as low as 100 170 K, the slow hydrogen bond exchange regime is usually reached where NMR signals of different acid base complexes being in equilibrium with each other are well resolved, a circumstance which increases considerably the informative power of liquid state NMR. As a result of this work, we succeeded in nding and assigning NMR features of several hydrogen-bonded species being present in the solutions in chemical equilibrium, in the slow hydrogen bond exchange regime. In this communication, the spectra of two of them, namely, AcO d2 H F21 d ([AcOHF]2) and AcOH F2 HOAc [(AcOH)2F]2 are described and characterized.

chemical shifts were measured using uoroform, CHF3 (CDF3), as internal standard, and were converted to the conventional TMS (tetramethylsilane) scale. The total deuterium fraction was determined by comparison of the integrated signal intensity of the residual mobile proton site with those of the immobile CH-protons. It should be noted that, as a rule, the resolution in our low-temperature spectra is much worse than in usual (ambient temperature) liquid state spectra. It is explained by a considerable viscosity of freon mixtures, and is markedly revealed in spectra of nuclei with high magnetic shielding anisotropy, like 19F.

3. Hydrogen bond correlations In order to link the NMR parameters of the hydrogen bonded FHO and OHFHO systems studied to hydrogen bond geometries we will make use of several hydrogen bond correlations, which have been established previously by various authors. To a given hydrogen bond of the type A H B one can normally associate two distances, r1 for the diatomic unit AH and r2 for the diatomic unit H B. According to Pauling [21], these distances correspond to the valence bond orders
0 p1 exp{ 2 r1 2 r1 =b1 };

2. Experimental 2.1. Materials A measured amount of 40% hydrouoric acid was added to a solution of TBA acetate (Aldrich) in dichloromethane (Aldrich). Then water was removed by repeated azeotropic distillation with dry dichloromethane. The H/D replacement of the mobile (OH, FH) proton was performed by dissolving a salt in methanol OD: proton/deuterium exchange between acetic acid uoride anion and excess of methanol leads to the partial substitution of H for D in the salt. Methanol was then removed under reduced pressure, leaving in the deuterated salt in the ask. The oily product was placed into a hermetic thick-walled NMR sample tube equipped with PTFE (polytetrauoroethylene) valves (Wilmad, Bueno), connected to a high vacuum line and lled with the solvent via vacuum transfer. The solvent, CDF3/CDF2Cl, with freezing point below 100 K was added to the samples by vacuum transfer. The approximate overall concentration of the samples, estimated by weighing chemicals and measuring the volume of the solution at low temperatures (around 120 K), was about 0.02 M. 2.2. NMR spectra The Bruker AMX-500 NMR spectrometer used was equipped with a low-temperature probe-head which allowed us to perform experiments down to 100 K. 1H and 19F NMR

0 p2 exp{ 2 r2 2 r2 =b2 }; with p1 p2 1:

For H, the total valence has to be unity. The correlation of r1 with r2 also implies a correlation between the hydrogen bond coordinates q1 1=2r1 2 r2 and q2 r1 r2 : For a linear hydrogen bond, q1 represents the distance of H from the hydrogen bond center and q2 the distance between atoms A and B. When H is transferred from one heavy atom to the other, q1 increases from negative values to positive values. q2 goes through a minimum which is located at q1 0 for AHA and near 0 for AHB systems. The parameters in Eq. (1) have been derived empirically from various experiments such as neutron diffraction or solid state NMR and the results of quantum-mechanical calculations. For the FH and OH bonds, the following parameters have been proposed [17,19], i.e.
0   r1 0:897 A and b1 0:360 A for HF and 0   r2 0:942 A; b2 0:371 A for OH:

0 0 r1 and r2 refer to the values of the hypothetical diatomic molecules. b1 and b2 describe the decrease of the bond orders with increasing distances. For the correlation of HF coupling constants in FHB systems, some of us have proposed the relation [20] 1 1

JFHB 1 JFH0 pFH 2 8DJFHBpFH p2 ; HB JFH0 600 Hz; 3

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with DJFHB 162:5 Hz for B F and DJFHB 190 Hz for B N. We will assume later that the average value is valid for B O, DJFHO 176 Hz: For the analysis of the 1H chemical shifts we use the relation

dFH dFH0 pFH dHB0 pHB 4DdFHBpFH pHB 4

The parameters A and B are empirical and will depend on the type of the hydrogen bond studied. We will use here the values A 220 and B 5 for the FHF and the FHO hydrogen bonded systems considered in this work. For a given set of values pFH and pOH one can calculate using Eq. (6) the corresponding values of pFD and pOD and hence the uorine chemical shifts of the deuterated systems. For this purpose, an appropriate simple computer program was written.

4. Results 4.1. NMR spectra at 120 K In Fig. 1 are depicted the low-eld 1H NMR signals of solutions TBA acetate (AcO2) with hydrogen uoride, with acetate/HF ratios of 3:1 (top) and 3:2 (bottom) and the deuterium fractions xD 0 (top) and xD 0:7 (bottom) in the hydrogen bonded sites. The upper spectrum exhibits two intense singlets at 19.3 and 16.5 ppm, which are typical for the acetic acid acetate homoconjugated anions labeled here as [OHO]2 and [OHOCOHO]2. These anions have been characterized recently; they are subject to a fast acetate acetic acid interconversion as revealed by 13C NMR [19]. In addition, we nd two doublets, exhibiting chemical shifts of 18.33 and 15.58 ppm and spin spin coupling constants 1 JFH near 60 Hz at 120 K. These signals were assigned to the anions [AcOHF] 2 ; [FHO] 2 and [(AcOH)2F]2 ; [OHFHO]2 as indicated in Fig. 1. As shown in the lower spectrum, two new signals appear at

dF dFH pFH dF pHB

8DdFHBpFH p2 HB

Here, we set for B O DdFHO 100 ppm; dF1 2100 ppm and dFH0 2210 ppm: We note that these parameters are not hard parameters but may change, when further experimental and theoretical results will be available. Therefore, one has to keep in mind that geometries derived using these equations from NMR parameters might be subject to systematic errors. However, they are sufcient for qualitative comparison of different Hbonded systems. Finally, we assume the following relations between the valence bond orders of the deuterated and the protonated hydrogen bonds

Dp pFH 2 pFD 2 pOH 2 pOD ApFH pOH B pFH 2 pOH ; pFH pOH pFD pOD 1: 6

Fig. 1. Low-eld part of 1H NMR spectra of solutions of tetrabutylammonium acetate and hydrogen uoride in CDF3/CDF2Cl at 120 K. Top: molar ratio 3:1, deuterium fraction in the hydrogen bond sites xD 0: Bottom: molar ratio 3:2, xD 0:7:

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Fig. 2. 19F NMR signals of solutions of tetrabutylammonium acetate and hydrogen uoride (molar ratio 3:2) in CDF3/CDF2Cl at 120 K. Left: signals of [OHFHO]2, L H, D at xD 0:73: Right: signals of [FHO]2 at xD 0:53:

16.8 and 15.84 ppm after partial deuteration, assigned to the complexes [OHOCODO]2 and [OHFDO]2. The assignment of [OHO]2 and [OHOCOHO]2 was based on the following observations: (i) a decrease of the acetate/HF ratio reduces the intensity of the low-eld signal, and that of the high-eld one is increased; (ii) partial H/D replacement does not alter the type of the low-eld signal, but produces a new peak for [OHOCODO]2 as mentioned above. This isotope shift has been labeled as a geometric vicinal isotope effect [19]. The assignment of the uorine containing species was done in a similar way. When the acetate/HF ratio is decreased, the intensity of the low-eld signal decreases, thus this signal has to be assigned to [FHO]2 and the high eld signal to [OHFHO]2. Again, partial H/D substitution reduces the intensity of the [FHO]2 signal, and introduces a new 1H signal for [OHFDO]2. The situation is analogous to the corresponding homoconjugate acetate acetic acid anions. Some typical 19F signals of samples partially deuterated in the hydrogen bond sites are depicted in Fig. 2. Signals of 1:1 complexes [FHO]2 and [FDO]2 are assigned by varying the deuterium fraction. The signals are broad and a scalar coupling with H is not resolved in the case of [FHO]2. The origin of this effect will be discussed later. The 19 F signals of [OHFHO] 2, [OHFDO] 2 and [ODFDO]2 are sharper, and appear at lower eld as indicated in Fig. 2. Only [OHFHO]2 and [OHFDO]2 exhibit a triplet and a doublet splitting with 1 JFH coupling constants of about 60 Hz as expected from the 1H spectra. Deuteration leads to a successive high-eld shift. Scalar couplings to D which should be of the order of 9 Hz are not resolved. All NMR parameters are collected in Table 1.

4.2. Variable temperature NMR spectra In order to elucidate the effect of temperature on the NMR parameters of the [FHO]2 and [OHFHO]2 clusters we have performed variable temperature measurements on samples of TBA acetate and HF mixture in CDF3/CDF2Cl which are depicted in Figs. 3 and 4. The 1H doublet of [FHO]2 shifts downeld and the one of [OHFHO]2 upeld as temperature is decreased; at the same time the 1 JFH splitting decreases. Both signals exhibit differential line widths of the doublet signal components, which are more pronounced at low temperatures. Generally, asymmetric doublets are caused by an interference between dipolar and chemical shift anisotropy relaxation mechanisms and an increase of the rotational correlation times t: For HF doublets, the low-eld component is broader than the higheld component if the coupling constant 1 JFH is positive and the high-eld component is broader than the low-eld

Table 1 Experimental NMR parameters of the 1:1 and 2:1 complexes of acetic acid with uoride in CDF3/CDF2Cl at 120 K NMR parameter [OHF]2 18.327 61.0 2132.21 2130.73 15.58 15.84 260.5 260.5 2108.64 2109.26 2109.90 [OHFHO]2

dFHO ^ 0:005 (ppm) 1 JFHO ^ 0:5 (Hz) dFHO ^ 0:01 (ppm) dFDO ^ 0:01 (ppm) dOHFHO ^ 0:01 (ppm) dOHFDO ^ 0:01 (ppm) 1 JOHFHO ^ 0:5 (Hz) 1 JOHFDO ^ 0:5 (Hz) dOHFHO ^ 0:01 (ppm) dOHFDO ^ 0:01 (ppm) dODFDO ^ 0:01 (ppm)

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Fig. 3. Variable temperature 1H NMR signals of [FHO]2 (left) and [OHFHO]2 (right) dissolved in CDF3/CDF2Cl. For further explanation see text.

component if 1 JFH is negative, as discussed previously [16,20]. Thus, we conclude that 1 JFHO . 0 and 1 JOHF HO , 0: At high temperatures, the line widths of the [OHFHO]2 species are larger than those of [FHO]2, a phenomenon which has to be assigned to the onset of hydrogen bond and proton exchange. At lower temperatures, the situation is inversed. Thus, [FHO]2 seems to be involved in a so far unresolved dynamic process. This process is better resolved in the 19F signals of this species, depicted in Fig. 4. The hydrogen bond exchange between the [FHO]2 and for [FDO]2 species is slow in the NMR time scale at the highest and lowest temperature accessible, and sharp lines are observed in both limits. At 170 K, doublet [FHO]2 is observed arising from scalar 1 JFH coupling. The splitting decreases with decreasing temperatures. Around 150 K, the lines are broadened and are shifted to low-eld. A maximum broadening is observed around 130 K, and then again a sharpening of the lines below this temperature. It is unlikely that these spectral features arise from transverse relaxation phenomena, for example from an increase of the uorine magnetic shielding anisotropy, effective especially at 130 K. By contrast, these spectral features are typical for the presence of an equilibrium between two species A and B, where A dominates at high and B at low temperatures, where the equilibrium constant is given by K xB =xA kAB =kBA : xA and xB are the mole fractions of both species and kAB and kBA are the rst-order or pseudo-rstorder rate constants of the interconversion. At 130 K, both

Fig. 4. Variable temperature 19F NMR signals of a mixture of [OHF]2 and [ODF]2 in CDF3/CDF2Cl. For further explanation see text.

N.S. Golubev et al. / Journal of Molecular Structure 700 (2004) 312

Fig. 5. Dependencies of the measured NMR parameters (chemical shifts and scalar spin spin coupling constants) for two clusters, [FHO]2 (left) and [OHFHO]2 (right), on temperature in the region, 110160 K.

species exhibit similar mole fractions, and in addition, the exchange rate constants kAB < kBA are by chance of the order of the chemical shift difference in Hz of the exchanging species, pnA 2 nB : As the values of ni are temperature dependent, we did not try to perform a quantitative line shape analysis. However, for 130 K we can estimate kAB < kBA < pnA 2 nB roughly to be about 300 s21. We note that this interconversion does neither lead to a collapse of spinspin splitting nor of the isotope splitting. This means, that the process does not involve proton nor hydrogen bond exchange. On the other hand, we note that the equilibrium constant K has to change strongly with temperature in order to produce a complete transformation of form B to form A within 20 K. This indicates a very large negative entropy and a very large negative enthalpy of the transition A ! B: Finally, in Fig. 5 we have plotted the 1H chemical shifts and 1 JHF coupling constants of [FHO]2, [OHFHO]2 and [OHFDO]2 as a function of temperature.

Data points for all variable temperature experiments are collected in Tables 2 and 3.

5. Discussion The above results show that acetic acid and uoride anion can form 1:1 and 2:1 clusters in polar solvent such as CDF3/CDF2Cl. In this section, we will rst link the NMR parameters of these clusters with the corresponding hydrogen bond geometries. We will then discuss the effects of H/D substitution as well as temperature dependent solvation on these geometries, in comparison with the clusters of HF with uoride, which have been studied previously [16,17]. Finally, the nature of the dynamic process in which the 1:1 complex is involved is discussed.

Table 2 1 H NMR parameters of the 1:1 and 2:1 complexes of acetic acid with uoride, [FHO]2, [OHFHO]2 and [OHFDO]2, in CDF3/CDF2Cl as a function of temperature T (K) [FHO]2 [OHFHO]2
1 JFHO (Hz)

[OHFDO]2
1 JFHO (Hz)

dFHO (ppm)
110 120 130 140 150 160 18.322 18.327 18.318 18.296 18.251 18.222

W1 (Hz) 80 43 23 27 28 25

W2 (Hz) 38 35 18 23 24 23

dFHO (ppm)
15.55 15.58 15.61 15.63 15.71 15.76

W1 (Hz) 24 16 18 42 70 70

W2 (Hz) 40 21 21 46 70 70

dFHO (ppm)
15.80 15.84 15.87

1 JFHO (Hz)

W1 (Hz) 25 16 27

W2 (Hz) 50 26 31

51.5 61.0 67.0 72.5 75.5 81.5

260.5 259.0 258.0 254.5 252.5 247.5

61.0 59.0 57.0

dFHO; chemical shift of the H-bond proton; W1 ; signal line width in Hz of the low-eld; W2 ; of the high-eld component.

N.S. Golubev et al. / Journal of Molecular Structure 700 (2004) 312 Table 3 19 F NMR parameters of the 1:1 acetate HF complex [FHO]2 in CDF3/CDF2Cl as a function of temperature T (K) H form D form W (Hz) 78 199 428 344 145 50 35

dFDO 2 dFHO (ppm)

dFHO (ppm)
110 120 130 140 150 160 170 2131.60 2132.21 2133.47 2134.82 2135.80 2136.60 2137.53

dFDO (ppm)
2129.86 2130.73 2132.21 2133.81 2135.02 2136.01 2137.19

W; signal line width.

5.1. Hydrogen bond geometries of [FHO]2 and [OHFHO]2 and their deuterated isotopologs In Fig. 6 we have depicted various geometric and NMR hydrogen bond correlations of the [FHO]2 and [OHFHO]2 clusters studied here. For comparison, we have included

those published previously for various hydrogen uoride uoride anions, [(FH)nF]2, where n 1 4: In Fig. 6a and f are depicted the correlations of the hydrogen bond coordinate, q1 1=2r1 2 r2 with q2 r1 r2 : As has been shown previously [16,17], the values obtained by ab initio calculations for [(FH)nF]2 are well located on the correlation curve, represented by the solid line in Fig. 6a. The geometric data in Fig. 6f were obtained empirically as described below. In Fig. 6b and g are depicted the values of the coupling constants 1 JFHB; B F, O as a function of q1 : As described previously both for FHF and FHN systems, a change of the sign of 1 JFHB is observed when H moved away from F just after crossing the H-bond center. After reaching a minimum, the coupling constants go to 0, because the FH distance becomes larger (obviously, the coupling constant is 0 at innite distance). In the case of the FHN systems we observed recently that the minimum was deeper as compared to FHF [20]. The same is true in the case of [FHO]2 and [OHFHO]2, we observe a similar sign change: the values of 1 JFHO are positive for [FHO]2 and negative for [OHFHO]2. The minimum value is again larger than the one for FHF. Assuming the validity of

Fig. 6. Hydrogen bond correlations of clusters of [(FH)nF]2 (left), adapted from Ref. [17] and of [FHO]2 and [OHFHO]2 (right). The solid lines correspond to the equations listed in the hydrogen bond correlations section. For further explanation see text.

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N.S. Golubev et al. / Journal of Molecular Structure 700 (2004) 312 Table 4 Hydrogen bond distances of [FHO]2 and [OHFHO]2 obtained by NMR Species [OHF]2 [OHF]2 [OHF]2 [OHF]2 [OHF]2 [OHF]2 [OHF]2 [ODF]2 [ODF]2 [ODF]2 [ODF]2 [ODF]2 [ODF]2 [OHFHO]2 [OHFHO]2 [OHFHO]2 [OHFHO]2 [OHFHO]2 [OHFHO]2 T (K) 110 120 130 140 150 160 170 110 120 130 140 150 160 110 120 130 140 150 160 rFH (A) 1.212 1.208 1.200 1.192 1.186 1.181 1.176 1.206 1.201 1.191 1.181 1.174 1.169 1.444 1.436 1.432 1.418 1.410 1.395 q2 (A) 2.234 2.353 2.351 2.350 2.349 2.348 2.347 2.353 2.351 2.349 2.348 2.347 2.346 2.477 2.472 2.469 2.460 2.455 2.444 q1 (A) 0.035 0.031 0.024 0.017 0.012 0.007 0.002 0.030 0.025 0.016 0.007 0.001 20.004 0.205 0.200 0.198 0.188 0.183 0.173 rOH (A) 1.142 1.145 1.151 1.158 1.162 1.167 1.171 1.147 1.151 1.158 1.167 1.173 1.178 1.034 1.036 1.037 1.041 1.044 1.049

Eq. (3), we obtain the solid line of Fig. 6g. Now, we could adjust the values of q1 in such a way that the experimental values of 1 JFHO are located on the correlation curve. Fixing the values of q1 determined also those of q2 in Fig. 6f. In Fig. 6c and h are depicted the 1H chemical shifts of both types of systems, and the agreement with Eq. (4) is satisfactory. In Fig. 6d and i we have included the corresponding uorine chemical shifts. As these shifts are much more sensitive to the hydrogen bond geometries, they were used to ne tune the q1 values. The H/D isotope effects on the uorine chemical shifts, DdFHB dFDB 2 dF HB are included in Fig. 6e and j. They are well reproduced by the solid lines calculated using Eq. (6). Again, the data for the FHF system were taken from Ref. [17]. We note that the DdFHF values are negative for H close to F, and even for [FHF]2 a negative value of 2 0.32 ppm was found. In our case, the values for [FHO]2 are positive, a result which can be taken as indication that H is a little bit closer to O than to F, although Fig. 6 indicates that [FHO]2 is very similar to the symmetric [FHF]2. By increasing temperature, the hydron in [FHO]2 is shifted towards F, and at 160 170 K, a symmetric proton shared geometry is reached. Note, that there are no unusual spectral changes in this temperature region, which is not surprizing while for the asymmetric hydrogen bonds q1 0 does not correspond to any special physical situation. By contrast, the hydrons in [OHFHO]2 are closer to O than to the central uoride, in a similar way as in the corresponding cluster [FHFHF]2. Again, increasing temperature shifts both H towards F, but the centered H-bond is not reached at 160 K. As a motive power of this displacement, preferential solvation of compact uoride anion as compared to the acetate is proposed. All hydrogen bond distances estimated from the analysis of Fig. 6 are included in Table 4. These distances are affected by systematic errors, in view of many assumptions both concerning the forms of Eqs. (1) (6) as well as the parameters used. However, we think that relative changes are well reproduced, in particular the observed sign change of the coupling constants. The reasons for the temperature shifts have been discussed in previous papers [18 20]. As temperature is lowered, the local polarity increases because of solvent ordering around the solutes, and structures with larger dipole or quadrupole moments are favoured. In non-charged neutral hydrogen bonds, the zwitterionic structures are reached by shifting the proton towards or across the hydrogen bond center. In the case of ions, a nonsymmetrical charge distribution will lead to similar effects. The geometric changes of [FHO]2 with temperature as expressed in Fig. 6 and Table 4 are then the consequence of this phenomenon. Finally, we come to the discussion of the vicinal isotope effects [19,20] found previously for [FHFHF]2 and the [OHOCOHO]2 systems, and here for [OHFHO]2. This phenomenon implies that the chemical shift difference

dAHXDB 2 dAHXHB of a coupled hydrogen bonded system AHXHB is non-zero. This means that the chemical shift of H in AHX depends on whether the neighbouring bond XHB is protonated or deuterated. For [OHOCOHO]2 a value of 0.29 ppm was found (see Fig. 1 and Ref. [19]), a value which is very close to the one of 0.26 observed for [OHFHO]2 (Fig. 1 and Table 1). For comparison, the value of [FHFHF]2 is 0.155 ppm. These values indicate a mutual inuence of the two coupled hydrogen bonds in all the three systems which exhibit an anti-cooperativity. Thus, deuteration of XHB leads to an increase of the X B distance, but a decrease of the A X distance. In the case of anions, this feature is understandable and in terms of a higher charge on X as compared to A and B. When the donor HB moves away from X2, the latter becomes more basic and attracts the proton from AH, leading then to a distance increase of AH and a shortening of the A X distance. Thus, from vicinal isotope effects qualitative conclusions about the hydrogen bond structure can be obtained.
5.2. Structure and dynamics of [FHO]2 at low-temperature So far, we have only considered the geometry of the hydrogen bond in [FHO]2 but did not yet discuss the whole structure of this complex, which is characterized also by an orientational degree of freedom of the acetate moiety with respect to the HF moiety. In fact, using different techniques, rotational isomers have been detected previously for formic acid monomer in gas phase and for the complex of formic acid with hexamethylphosphorotriamide in polar solvents [22,23]. The rotational isomerism may be characterized by different COF angles b as depicted in Scheme 1 for two

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11

Scheme 1.

arbitrary values of b leading to two isomers C and D. Naturally, one could equally well conceive a broad distribution of angles b: The different congurations will exhibit different electrical properties, and therefore, by the interaction with the surrounding solvent molecules and the countercation isomers with larger dipole moments will be favoured at lower temperatures. Another degree of freedom arises from the possibility of a hydrogen bond ip of the HF moiety between the two oxygen atoms of acetate as indicated in Scheme 1. Especially form C will be subject to such a fast hydrogen bond ip, whereas the corresponding ip in form D will be slower. The ip may involve a transition state exhibiting a symmetric conguration with bifurcated hydrogen bond; however, such a symmetric structure cannot be excluded as main structure of the complex. Some of us have previously found evidence for similar very fast hydrogen bond ips in low-temperature solutions of hydrogen bonded complexes [24]. The question arises, whether the observed equilibrium between the high-temperature form A and the lowtemperature form B can be explained in terms of the reaction network of Scheme 1. A dominates at higher and B at lower temperatures which means that B should exhibit a larger dipole moment than A. At 130 K, the interconversion rate is about 300 s21. As mentioned above, the interconversion is not related to hydrogen bond breaking processes which would lead to a coalescence of the signals of [FHO]2 and [FDO]2, in contrast to the experimental ndings, nor to proton exchange, which would lead to a collapse of the 1 JFH O spin spin splitting pattern. On the other hand, from the graphs of Fig. 6 there is no evidence for major changes of the hydrogen bond geometry. Therefore, the process is also not related to proton jumps between two sites in the hydrogen bond, one closer to F and the other closer to O. These constraints as well as the simple molecular structure of [FHO]2 limit strongly the possibilities. Thus, as a preliminary working hypothesis, we tentatively assign A to C and B to D. An argument

against this assignment is that one expects very large rate constants of the interchange between forms C and D, in contrast to what is found for A and B experimentally. However, it may be that the dynamics of the interchange are determined by an unknown aggregation process involving not only complexes [FHO]2 but also solvent molecules and the countercation. Depending on the aggregation state, the angle b may adopt a preferential value. Authors would like to thank the referee for pointing out another mechanism, which could be responsible for the spectral changes shown in Fig. 4. In this mechanism A is CH3COOH F2 and B is CH3COO2 HF, which differ only by the average proton position, while the dynamic behaviour is attributed to the slow solvent reorganization that is needed to convert one of these forms to the other. This attribution is supported by the continuous change of average q1 values (see Table 4). Slow (in the NMR time scale) proton transfer, CH3COOH F2 $ CH3COO2 HF, can really be a reason of the observed NMR effects, but solvent reorganization as a process retarding the proton transfer is more than doubtful. Indeed, dielectric relaxation in non-viscous liquids takes usually the time as low as 10210 10212 s, and low viscosity of the used freon mixture at 120 140 K is proved by comparatively sharp NMR lines of the solvent. More probable seems to be the process of slowing down, shown in Scheme 2. Such interconversion involves not only proton transfer but also H-bond reorganization, which requires some activation energy for breaking down one of the hydrogen bonds. This hypothetical mechanism can be conrmed or rejected by a calculation of the whole reaction pathway.

Scheme 2.

12

N.S. Golubev et al. / Journal of Molecular Structure 700 (2004) 312 [5] C. Viragh, T.K. Harris, P.M. Reddy, M.A. Massiah, A.S. Mildvan, I.M. Kovach, Biochemistry 39 (2000) 16200. [6] Y. Kim, K.H. Ahn, Theor. Chem. Acc. 106 (2001) 171. [7] D.B. Northrop, Acc. Chem. Res. 34 (2001) 790. [8] W.W. Cleland, Arch. Biochem. Biophys. 382 (2000) 1. [9] K.B. Schowen, H.H. Limbach, G.S. Denisov, R.L. Schowen, Biochim. Biophys. Acta 1458 (2000) 43. [10] B.A. Katz, J.R. Spencer, K. Elrod, C. Luong, R.L. Mackman, M. Rice, P.A. Sprengeler, D. Allen, J. Janc, J. Am. Chem. Soc. 124 (2002) 11657. [11] P.A. Frey, J. Mol. Struct. 615 (2002) 153. [12] (a) A. Warshel, A. Papazyan, P.A. Kollman, Science 269 (1995) 102. (b) A. Warshel, A. Papazyan, Proc. Natl Acad. Sci. USA 93 (1996) 13665. (c) A. Warshel, J. Biol. Chem. 273 (1998) 27035. (d) C.L. Perrin, J.B. Nielson, Annu. Rev. Phys. Chem. 48 (1997) 511. [13] C.J. Smallwood, M.A. McAllister, J. Am. Chem. Soc. 119 (1997) 11277. [14] G.A. Kumar, Y. Pan, C.J. Smallwood, M.A. McAllister, J. Comput. Chem. 19 (1998) 1345. [15] N.S. Golubev, I.G. Shenderovich, P.M. Tolstoy, D.N. Shchepkin, J. Mol. Struct. (2004) (in press). [16] I.G. Shenderovich, S.N. Smirnov, G.S. Denisov, V.A. Gindin, N.S. Golubev, A. Dunger, R. Reibke, S. Kirpekar, O.L. Malkina, H.-H. Limbach, Ber. Bunsen. Phys. Chem. 102 (1998) 422. [17] I.G. Shenderovich, H.-H. Limbach, S.N. Smirnov, P.M. Tolstoy, G.S. Denisov, N.S. Golubev, Phys. Chem. Chem. Phys. 4 (2002) 5488. [18] I.G. Shenderovich, A.P. Burtsev, G.S. Denisov, N.S. Golubev, H.-H. Limbach, Magn. Res. Chem. 39 (2001) S1/91. [19] P.M. Tolstoy, P. Schah-Mohammedi, S.N. Smirnov, N.S. Golubev, G.S. Denisov, H.-H. Limbach, J. Am. Chem. Soc., submitted for publication. [20] I.G. Shenderovich, P.M. Tolstoy, N.S. Golubev, S.N. Smirnov, G.S. Denisov, H.-H. Limbach, J. Am. Chem. Soc. 125 (2003) 11710. [21] (a) L. Pauling, J. Am. Chem. Soc. 69 (1947) 542. (b) I.D. Brown, Acta Crystallogr. B48 (1992) 553. [22] E. Bjarnov, W.H. Hocking, Z. Naturforsch. 33A (1978) 610. [23] N.S. Golubev, E.G. Pushkareva, Vestnik LGU 11 (1985) 87. [24] F. Mannle, H.-H. Limbach, G.S. Denisov, J. Am. Chem. Soc., submitted for publication.

6. Conclusions We have shown that using low-temperature NMR it is possible to detect non-trivial properties of simple hydrogen bonded clusters of uoride with carboxylic acid. As uoride and hydroxide have many similarities, this work may also be interesting for modeling complex hydrogen bonded networks in functional biomolecules. Using the valence bond order correlations, it is possible to link the worlds of NMR parameters and hydrogen bond geometries, and obtain information about the effects of a polar solvent on the latter. We hope that such results will stimulate further theoretical work in this area of research.

Acknowledgements This work is nancially supported by the Russian Foundation for Basic Research, Grants 03-03-32272 and 03-03-04009, the Deutsche Forschungsgemeinschaft, Bad Godesberg, and the Fonds der Chemischen Industrie, Frankfurt. P.M.T. thanks the Fonds for a Kekule scholarship. Authors are grateful to the referee for valuable comments and suggestions.

References
[1] W.W. Cleland, M.M. Kreevoy, Science 264 (1994) 1887. [2] P.A. Frey, S.A. Whitt, J.B. Tobin, Science 264 (1994) 1927. [3] N.S. Golubev, G.S. Denisov, V.A. Gindin, S.S. Ligay, H.-H. Limbach, S.N. Smirnov, J. Mol. Struct. 322 (1994) 83. [4] A.S. Mildvan, M.A. Massiah, T.K. Harris, G.T. Marks, D.H.T. Harrison, C. Viragh, P.M. Reddy, I.M. Kovach, J. Mol. Struct. 615 (2002) 163.