4686
Inorg. Chem. 1988, 27, 4686-4691
formula unit could enter the channels. The introduction of this new atom in the structure did not open any gaps in the total density of states, and the new material should still be metallic. Acknowledgment. M.J.C. is grateful to the Calouste Gulbenkian Foundation for its support of her stay at Cornell. M.J.C. also thanks Marja Zonnevylle and Jing Li for sharing their expertise and for helpful discussions. Our work was supported by the National Science Foundation, Grant DMR 821722. We thank Jane Jorgensen and Elisabeth Fields for the drawings and Joyce Barrows for the production of the manuscript. Appendix All of the calculations were of the extended Huckel type,9 with
the tight-binding approach.I0 The parameters used are collected in Table IV. The geometry of Ni2Ta9S61*2 was used as the undistorted structure. In the study of distortion the same unit cell parameters a and c' = 2c were taken, but the general positions of the atoms in Fe2Ta9S6were used. The k-point sets were chosen according to the size of the unit cell, using the method of Ramirez and BOhm.l9 Registry No. Fe2Ta9S6,101238-71-5;Co2Ta9S6,101238-67-9; Ni2Ta9S6,101238-83-9;S, 7704-34-9. (19) Ramirez,
R.; Bohm, M. C. Inr. J. Quantum Chem.
1986, 30,
391.
Contribution from the Laboratory of Organic Chemistry, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands
Multinuclear NMR Study of Lanthanide(II1) Complexes of Diethylenetriaminepentaacetate Joop A. Peters Received January 20, 1988
The complexation of lanthanide(II1)cations with diethylenetriaminepentaacetate (DTPA) in the presence of lithium as counterion in aqueous solution has been investigated with the use of "C, "0, and 6Li NMR shift and relaxation measurements. The data show that the DTPA ligand is bound octadentately via the three nitrogens and the five carboxylates. Conformational interconversions, taking place in the DTPA ligand, give rise to exchange broadening in the I3C and 'H NMR spectra. The first coordination sphere is completed by one water, while two lithium counterions are present in the second coordination sphere. The counterions are probably exchanging between the various carboxylate groups. Introduction
The paramagnetic lanthanide(II1) ions have a pronounced influence on the chemical shifts and relaxation rates of nuclei in their The enhancement of longitudinal and transverse relaxation rates by, particularly, Gd"' has been successfully applied to improve contrast in magnetic resonance imaging. In order to reduce its toxicity, the Gd"' in contrast agents is bound by a very strong chelator such as diethylenetriaminepentaacetate (DTPA).4s5 a'coo-
YOO-
\CH, \N, '/
'CH,
/ -
bCOO
* I /
CH
2- CH ph- N '- C H
/CH,
-C: H2
h'
2
Pi,"
/
e'CH2
Acoo-
b
The X-ray crystal structure determinations of Na2Gd(DTPA).H206 and BaNd(DTPA).3H207revealed that in the solid (1)
Sherry, A. D.; Geraldes, C. F. G. C. In Lanthanide Probes in Lve,
Medical, and Environmental Sciences: Theory and Practice; Biinzli, J.-C., Choppin, G. R., Eds.; Elsevier: Amsterdam, 1988; Chapter 3. (2) Inagaki, F.; Miyazawa, T. Prog. Nucl. Magn. Reson. Spectrosc. 1981, 14, 67. (3) Peters, J. A.; Kieboom, A. P. G. Red. Trav. Chim. Pays-Bas 1983, 102, 381.
(4) Laniado, M.; Weinmann, H. J.; Schorner, W.; Felix, R.; Speck, U. Physiol. Chem. Phys. Med. N M R 1984, 16, 157. ( 5 ) Goldstein, E. J.; Burnett, K. R.; Hansell, J. R.; Casaia, J.; Dizon, J.; Farrar, B.; Gelblum, D.; Wolf, G. L. Physiol. Chem. Phys. Med. NMR 1984, 16, 91. ( 6 ) Gries, H.; Miklautz, H. Physiol. Chem. Phys. Med. NMR 1984, 16, 105.
0020-1669/88/1327-4686$01.50/0
state the Ln"' cation is coordinated to the three nitrogens and five carboxylate oxygens of DTPA and to a water. Several studies of the coordination of DTPA by Ln"' cations have been reported. Both hep@s9 and octadentate have been proposed for the DTPA ligand, and it has been shown that in solution one water is coordinated to the Ln"' ~ a t i o n . ' ~ ~ ' ~ J ~ This paper reports the results of a multinuclear N M R study on the structure of Ln"'-DTPA complexes in aqueous solution. Chemical shifts and Nd"'-induced 13Crelaxation rate enhancements were used to determine the denticity of the DTPA ligand and to obtain information on its structure, whereas Ln"'-induced 170water shifts were employed to determine the water coordination number. In order to get an impression about the location of the monovalent counterions near the negatively charged Ln"'-DTPA complex, 6Li N M R techniques were applied. Experimental Section The LnC13-xH20salts were purchased from Alfa Products. The Ln"' content was determined by an EDTA titration using arsenazo I as the indicator. The DTPA used was obtained as the acid (H,(DTPA)) from Fluka A.G. The solutions used in this study were prepared by dissolving H5(DTPA)in a solution of an equivalent amount of LiOH in D20. Then the Ln"'saIt was added, and the pD was adjusted with DCI or LiOH in D20. (7) Stezowski, J. J.; Hoard, J. L. Isr. J . Chem. 1984, 24, 323. (8) Choppin, G. R.; Baisden, P. A.; Khan, S. A. Inorg. Chem. 1979, 18, 1330. (9) Geraldes, C. F. G. C.; Sherry, A. D. J . Magn. Reson. 1986, 66, 214. (10) Alsaadi, B. M.; Rossotti, F. J. C.; Williams, R. J. P. J . Chem. Soc., Dalron Trans. 1980, 2 15 1. (11) Kostromina, N. A.; Ternovaya, T. V. Russ. J . Inorg. Chem. (Engl. Trawl.) 1979, 24, 1024. (12) Bryden, C. C.; Reilley, C. N. Anal. Chem. 1982, 54, 610. (13) Koenig, S. H.; Baglin, C.; Brown, R. D., 111; Brewer, C. F. Magn. Reson. Med. 1984, I , 497.
0 1988 American Chemical Society
Multinuclear N M R Study of Ln"'-DTPA
Inorganic Chemistry, Vol, 27, No. 26, 1988 4681
Complexes
Table I. 13C N M R Shifts" of Ln(DTPA)2- ComDlexes in D,Ob at DD 7 and 73 OCC ~~
Ln La Ce Pr Nd Sm
Eu Tb Lu
C(a,a') 181.60 193.56 201.73 180.28 187.59 184.33 336 181.86
C(b,b') 182.32 186.81 185.45 180.86 187.59 183.33 287 182.46
C(C) 182.12 170.16 166.25 168.97 187.79 203.84 18 181.48
C(d,d') 64.87 72.92 74.92 65.69 70.23 69.72 218 65.01
C(e,e') 64.87 80.49 89.07 68.64 69.16 70.71 327 65.01
C(f) 66.57 53.17 45.99 52.88 66.69 96.07 -0 65.69
C(g,g') 59.1 1 46.06 30.18 32.60 58.23 99.48 -0 59.61
C(h,h') 57.71 36.10 13.45 24.59 56.68 114.82 -151 57.70
OIn ppm; internal standard rerf-butyl alcohol (CH,:31.20 ppm). bMeasured from samples obtained upon adding Ln"' to a 0.13 M solution of Li5(DTPA) in D 2 0 ; p = 0.7. CTheassignments of the signals are described in the section "Lanthanide-Induced "C N M R Shifts". Those of the I3C nuclei of the terminal acetate groups might be interchanged. This assignment is leading to the optimum fit between observed and calculated G values (see text). All N M R spectra were recorded with a Nicolet NT-2OOWB spectrometer using 12-mm sample tubes. The 170N M R spectra were measured by using 4K data points, IO-kHz spectral width, and a repetition rate of 205 ms. Usually 1000 transients were needed to obtain a good signal-to-noise ratio. The chemical shifts (I7O) were determined by fitting the signal with a Lorenzian line function. The 170chemical shifts were determined with respect to D 2 0 as external standard, and the 6Li chemical shifts, with respect to 5 M LiCl in D 2 0as external standard. For 13Cand ' H N M R , tert-butyl alcohol was used as internal standard (31.2 and 1.20 ppm, respectively). Downfield induced shifts are denoted as positive. Longitudinal relaxation rates were measured by using a [(90°,1 80°y900,)-~-900-acq] inversion recovery pulse sequence. The ]/TI values were calculated by using a three-parameter fit of the experimental data.14 The transverse relaxation rates were calculated from the line widths at half-height by way of the relation 1/T2 = 7 r A ~ ~ / ~ . These line widths were determined by fitting the N M R signals with a Lorenzian line function. For the Nd"'-DTPA complexes it was established that the I3C N M R spectra were invariant in the range pH 3-9. At pH
