53Cr Fourier Transform Nuclear Magnetic Resonance Studies B

53Cr Fourier Transform Nuclear Magnetic Resonance Studies B. W. Epperlein, H. Krüger, 0. Lutz, and A. Nolle

Physikalisches Institut der Universität Tübingen

and W. Mayr

Chemisches Institut der Universität Tübingen, Germany

(Z. Naturforsch. 30 a, 1237-1240 [1975]; received July 12, 1975)

In various alkali Chromate solutions in H20 and D20 the dependence of the Larmor frequency of 53Cr on the concentration of the solutions was measured by Fourier transform NMR and a large solvent isotope effect on the chemical shift of 53Cr was found. Further in potassium Chromate

solutions the chemical shifts of 39K were observed and in a 2.2 molal solution of K2Cr04 in D20 a ratio of the Larmor frequencies of 53Cr and of 39K was measured with high accuracy. Using the concentration dependence of the Larmor frequencies of 53Cr and of 39K, an extrapolated ratio

v (53Cr) /r (39K) extrapol. in infinitely diluted K2Cr04 in D20 is given. From this ratio a value of the magnetic moment of 53Cr in the Chromate ion is derived. In chromium hexacarbonyl the 53Cr signal was observed and the chemical shift is given.

I. Introduction in D20 Halbach 8 verified, that the nuclear spin of 53Cr is 3/2. Using the Fourier-Transform NMR method112 In an other 53Cr NMR experiment Egozy and Loe- systematic investigations of nearly all stable isotopes wenstein9 measured the exchange rate in the chro- with a nuclear spin are possible, also of the isotopes mate-dichromate system. Further Barnes and Gra- of the transition elements in their diamagnetic com- ham 10'11 determined the Knight shift of 53Cr in pure pounds. For transition elements usually very large chromium metal and in V — Cr alloys, relative to the chemical shifts are observed 3 and, since most of the Na2Cr04 solution given in Reference 6. isotopes have quadrupole moments, the linewidths In this work the dependence of the Larmor fre- have a large range, f.e. in Mn compounds 4. There- quency of 53Cr on the concentration of diverse alkali fore one of the first problems is to choose an ap- Chromates in H20 and D20 was investigated. The propriate reference compound. chemical shift of 53Cr in chromium-hexacarbonyl in To proceed with NMR investigations in different tetrahydrofuran was determined and the NMR sig- 53 groups of the periodic table we have studied Cr nals of 53Cr of some various chromate-dichromate 53 NMR signals. The 9.5% naturally abundant Cr is systems were observed. Further a ratio of the Lar- the only chromium isotope which has a nonzero mor frequencies of 53Cr and of 39K in a K2Cr04 spin I = 3/2. In a 1 molal solution of K2Cr04 in H20 solution was measured. By these results a new value the relative sensitivity of 53Cr is 7.9 • 10-7 compared of the magnetic moment of 53Cr in a Cr042- ion sur- with 1 for the proton NMR signal in this solution rounded only by water molecules can be given. Solu- without considering the relaxation times. This is the tions of Na2Cr04 or K2Cr04 are proposed as refer- 53 reason that for Cr only a few NMR measurements ence standards for the 53Cr NMR investigations. are known 5-11. The magnetic moment of 53Cr in the Chromate ion was determined in two different experi- ments in 1953 5'6. Woonton and Dyer7 got a value II. Experimental of the magnetic moment of 5^Cr in a MgO crystal by 53 an ENDOR experiment. The accuracy of these mag- The Cr measurements were done with a commercial multinuclei Bruker pulse spectrometer netic moments is about 1 • 10-4 or worse. By com- SXP 4-100 in a magnetic field of 2.1 T produced by 53 paring the intensity of the Cr NMR signal in a a Bruker 15" magnet system. The magnetic field was 2 Na2Cr04 solution with the intensity of the H signal externally stabilized by the Bruker NMR stabilizer B-SN 15. The free induction decays of 53Cr and of Reprint requests to Prof. Dr. 0. Lutz, Physikalisches 39K were accumulated and Fourier transformed by Institut der Universität Tübingen, D-7400 Tübingen, Morgenstelle. the Bruker BNC 12 computer.

Dieses Werk wurde im Jahr 2013 vom Verlag Zeitschrift für Naturforschung This work has been digitalized and published in 2013 by Verlag Zeitschrift in Zusammenarbeit mit der Max-Planck-Gesellschaft zur Förderung der für Naturforschung in cooperation with the Max Planck Society for the Wissenschaften e.V. digitalisiert und unter folgender Lizenz veröffentlicht: Advancement of Science under a Creative Commons Attribution Creative Commons Namensnennung 4.0 Lizenz. 4.0 International License. 1238 B. W. Epperlein et al. • 53Cr Fourier Transform Nuclear Magnetic Resonance Studies 1238

53 The Larmor frequency of Cr was approximately 53Cr CHEMICAL SHIFTS at 5.09 MHz 5.0875 MHz, that of 39K about 4.1999 MHz. Both Larmor frequencies can be observed with the de- scribed spectrometer by retuning without apparative alterations. The ratio of the Larmor frequencies v(53Cr)/v(39K) was measured in a 2.2 molal K2Cr04 solution in D20 in a rotating cylindrical sample tube of 10 mm outer diameter. Most of the chemical shift measurements were performed in nonrotating cylindrical tubes (10 mm outer diameter). Only for the measurements of K2Cr04 solutions in D20 nonrotating cylindrical and spherical tubes of 10 mm outer diameter were used. The temperature was (299 ± 2)K. Signal-to-noise ratios of about 40 were achieved for 53Cr within 5 minutes of measuring time and for 39K signal-to-noise ratios of 100 within about 1 min- ute in the 2.2 molal K2Cr04 solution in D20. A Fig. 2. Chemical shifts of 53Cr in diverse aqueous solutions typical absorption curve is given for 53Cr in Figure 1. of chromium salts as a function of concentration. Cylindrical The linewidths were about 11 Hz for 53Cr and samples of 10 mm outer diameter were used. The shifts are 12 Hz for 39K in this solution. referenced to the extrapolated frequency of the infinite dilution resonance of 53Cr in the chromate ion for water. — The chemical shift is given by d = ^sampie No bulk susceptibility corrections were made. ^reference > a positive value means a shift to higher frequency at a constant field.

The shifts are referenced to the extrapolated fre- quency of the infinite dilution resonance of 53Cr for HoO. Increasing the concentration of the solutions one gets shifts to lower frequencies. Further the amount of the shifts is increasing in the sequence of

the cations: Na+, K+, Rb+, NH4+, Cs+. Comparing these results with measurements at other nuclei in oxy-anions one finds a similar behav-

iour in the case of 35C1 in C104~ 12 and of 55Mn in

Mn04~13. Because of the small sensitivity of the 33S 14 and of the 183W NMR signal15 the accuracy of

Fig. 1. Absorption signal of 53Cr in a 2.2 molal solution of the results in the corresponding oxy-anions S042~ K2Cr04. Larmor frequency: 5.087 519 MHz, line width: and W042~ is too small to show differences of the 11 Hz, spectrum width: 1000 Hz, pulse repetition frequen- cy: 3.3 Hz, accumulation time: 5 min, number of pulses: Larmor frequencies in solutions containing different 1000, rotating cylindrical sample: 10 mm outer diameter, alkali cations. sample volume: 1.5 ml. For getting the influence of the bulk susceptibility

the chemical shifts of K2Cr04 in D20 have been measured as well in spherical as in cylindrical III. Results and Discussion sample tubes. The results are given in curve c and b a) Chemical shifts of 53Cr in aqueous solutions of Figure 3. The Larmor frequency in a spherical of alkali Chromates tube is shifted to lower frequency and the gradient is a little smaller than in the cylindrical sample The dependence of the Larmor frequency of 53Cr tubes. But there is still a dependence of the Larmor on the concentration of the alkali Chromates in frequency of 53Cr on the concentration of the K2Cr04 aqueous solutions, excepted the lithium chromate solution. It seems reasonable, to take solutions of because of its small solubility in water, has been Na2Cr04 or K2Cr04 in H20 as reference standards investigated. The results are given in Figure 2. for further 53Cr NMR investigations, because in B. W. Epperlein et al. • 53Cr Fourier Transform Nuclear Magnetic Resonance Studies 1239 these solutions only small chemical shifts must be on the alkali cations, but the linewidths are very taken into consideration and because in these solu- sensitive to variations of the pn-value: The pa-value tions relatively strong and small NMR signals can of a 2 molal solution of K2Cr04 is about 9. If acid be achieved. is added, Cr2072~ is formed and the observed line- width is increasing to a value of 80 Hz for pn = 6.9.

The 53Cr NMR line in a 2 molal Na2Cr207-solution 53 Hz A Chemical Shift Cr at 5.09 MHz (pn = 3.5) was not detected. Similar results were found by Egozy and Loewenstein9. A remarkable Concentration shift of the Larmor frequency was not observed in solutions with different pn-values.

d) Chemical Shift of 53Cr in chromium-hexacarbonyl The 53Cr signal has been found not only in the

oxidation state + 6 in the Cr042- ion but also in the

oxidation state 0 in the Cr(CO)6 compound. In Figure 4 an absorption signal of 53Cr in this com- pound is given. The chemical shift of a 0.14 molal solution in tetrahydrofuran relative to the chromate

ion in infinite dilution in H20 is — (1795 ± 3) ppm. Measurements of other chromium complexes are running.

Fig. 3. Chemical shifts of 53Cr in different potassium Chromate solutions as a function of concentration. The measurements of the curves a and b were performed in cylin- drical samples of 10 mm outer diameter in H20 respectively in DoO. The points of curve c were measured in spherical samples of 10 mm outer diameter. The shifts are referred to the Larmor frequency of 53Cr in the Chromate ion sur-

rounded only by H20 molecules.

b) Solvent Isotope Effect

The Larmor frequency of a nucleus in aqueous Fig. 4. Absorption signal of 53Cr in a 0.14 molal Cr(CO)6 solution in tetrahydrofuran. Larmor frequency: 5.078 290 solutions usually depends on the isotopic composi- MHz, line width: 17 Hz, spectrum width: 1000 Hz, pulse tion of the solvent. Curves a and b of Fig. 3 show repetition frequency: 10 Hz, accumulation time: 3.3 h, the difference of the Larmor frequencies of solutions number of pulses: 120 000, cylindrical sample of 10mm outer diameter, sample volume: 1.5 ml. of K2Cr04 in H20 and D20 for cylindrical sample tubes. This difference of the Larmor frequencies depends only a little on the concentration of the e) 39K chemical shifts in K2CrOA aqueous solutions solution and one gets for infinitely diluted solutions: In the case of the 39K resonance lines a nearly [>(53Cr in D20)/v(53Cr in H20) ] - 1 = (1.3 ± 0.3) linear dependence of the Larmor frequency on the ppm. This solvent isotope effect shows a negative concentration of solutions of K2Cr04 in D20 was sign, as it is usually observed 16, and the amount is found in cylindrical sample tubes. Relative to an comparable with the solvent isotope effect of 55Mn infinitely diluted K2Cr04 solution the 2.2 molal solu- in KMn04 solutions 13. tion, used for the measurements of the ratio of the Larmor frequencies v(53Cr)/v(39K), showed a chemi- c) Chromate-Dichrornate System cal shift of — (8+ 1) Hz. By measuring the Larmor The linewidths of 53Cr in aqueous alkali chromate frequency of the standard probe * of Ref.17, one solutions are in the range of 10 — 15 Hz and depend * We thank Dr. W. Sahm and Dr. A. Schwenk for their 2- only slightly as well on the Cr04 concentration as 39K standard sample, a 32 molal KN02 in H20. 1240 B. W. Epperlein et al. • 53Cr Fourier Transform Nuclear Magnetic Resonance Studies 1240 finds, that the 39K Larmor frequency in diluted 0.303 984 80(10) given in Ref. 17 and J'(2H)/v(1H) 19 K2Cr04 in D,0 is the same as that given for other = 0.153 506 083 (60) of a ratio infinitely diluted potassium solutions in D20 in r^CO/r^H) =0.056 524 773(34) Reference 17. Bloor and Kidd18 found a linear dependence of the Larmor frequency of 39K in can be given.

K2Cr04 of — 0.25 ppm per moles K+/1000 g solvent Using this ratio and the value of the magnetic on the concentration. The result reported in this moment of the proton in H20 /

1 R. R. Ernst and W. A. Anderson, Rev. Sei. Instrum. 37, 11 R. G. Barnes and T. P. Graham, Phys. Rev. Letters 8, 93 [1966]. 248 [1962]. 2 A. Schwenk, Z. Phys. 213, 482 [1968]. 12 J. Blaser, 0. Lutz, and W. Steinkilberg, Z. Naturforsch. 3 J. W. Emsley, J. Feeney, and L. H. Sutcliffe, High 27 a, 72 [1972]. Resolution Nuclear Magnetic Resonance Spectroscopy, 13 O. Lutz and W. Steinkilberg, Z. Naturforsch. 29 a, 1467 Vol. II, Pergamon Press, London 1966. [1974]. 14 4 F. Calderazzo, E. A. C. Lücken, and D. F. Williams, J. O. Lutz, A. Nolle, and A. Schwenk, Z. Naturforsch. 28 a, Chem. Soc. A 1967, 154. 1370 [1973]. 15 5 C. D. Jeffries and P. B. Sogo, Phys. Rev. 91, 1286 J. Bande and A. Schwenk, Z. Phys. B 20, 75 [1975]. 16 B. W. Epperlein, H. Krüger, O. Lutz, and A. Schwenk, [1953]. Z. Naturforsch. 29 a, 660 [1974]. 8 F. Alder and K. Halbach, Helv. Phys. Acta 26, 426 17 W. Sahm and A. Schwenk, Z. Naturforsch. 29 a, 1754 [1953]. [1974]. 7 G. A. Woonton and G. L. Dyer, Can. J. Phys. 45, 2265 18 E. G. Bloor and R. G. Kidd, Can. J. Chem. 50, 3926 [1967]. [1972]. 8 K. Halbach, Helv. Phys. Acta 27, 259 [1954]. 19 B. Smaller, Phys. Rev. 83, 812 [1951]. 9 Y. Egozy and A. Loewenstein, J. Mag. Res. 1, 494 20 E. R. Cohen and B. N. Taylor, J. Phys. Chem. Ref. Data [1969]. 2. 663 [1973]. 10 T. P. Graham and R. G. Barnes, Bull. Amer. Phys. Soc. 21 W. B. Mims, G. E. Devlin, S. Geschwind, and V. Jac- 7, 227 [1962]. carino, Phys. Letters 24 A, 481 [1967].