TY - JOUR
T1 - The solution structure of Ln (DOTP)5- complexxes. A comparison of lanthanide-induced paramagnetic shifts with the MMX energy-minimized structure
AU - Geraldes, Carlos F G C
AU - Sherry, A. Dean
AU - Kiefer, Garry E.
N1 - Funding Information:
The portion of this work performed at UT-Dallas was supported in part by grants from the Robert A. Welch Foundation (Grant AT-584) and Mallinckrodt, Inc. That portion of the work done by G.E.K. was supported solely by Dow Chemical Co., C.F.G.C.G. acknowledges support from the Luso-American Foundation for Development and I.N.I.C. (Portuguese Ministry of Education). The authors thank Drs. Don Woessner and Jim Gleason of Mobil Oil Co. for running several proton spectra on their Bruker MSL-200.
PY - 1992/4
Y1 - 1992/4
N2 - Complexes between the trivalent lanthanide ions and the macrocyclic chelate 1,4,7,10-tetraazacyclododecane-N,N′,N″,N‴-tetra(methylene phosphonate) (DOTP) have been examined by high-resolution NMR spectroscopy. The proton spectra of the diamagnetic La(DOTP)5- and Lu(DOTP)5- complexes provide evidence for very rigid chelate structures with the ethylenediamine-containing chelate rings essentially locked into a single conformation at room temperature. The activation energy for ethylenediamine chelate ring interconversions in these complexes is approximately 100 kJ mol-1, considerably higher than that reported previously for the corresponding Ln(DOTA)- complexes (DOTA is the tetraacetate analog of DOTP). Lanthanide-induced shifts are reported for all 1H, 13C, and 31P nuclei in 11 Ln(DOTP)5- complexes. The proton spectra of these complexes display unusually large lanthanide-induced shifts, one showing a spectrum in which the 1H resonances span 900 ppm. The contact and pseudocontact contributions to these shifts were separated using Reilley's temperature-independent method and the resulting pseudocontact lanthanide-induced NMR shifts were in excellent agreement with those calculated for a structure derived using MMX molecular modeling methods. The pseudocontact shifts provide evidence for Ln (DOTP)5- chelates which have virtually identical structures along the lanthanide series, with the possible exception of Tm(DOTP)5-.
AB - Complexes between the trivalent lanthanide ions and the macrocyclic chelate 1,4,7,10-tetraazacyclododecane-N,N′,N″,N‴-tetra(methylene phosphonate) (DOTP) have been examined by high-resolution NMR spectroscopy. The proton spectra of the diamagnetic La(DOTP)5- and Lu(DOTP)5- complexes provide evidence for very rigid chelate structures with the ethylenediamine-containing chelate rings essentially locked into a single conformation at room temperature. The activation energy for ethylenediamine chelate ring interconversions in these complexes is approximately 100 kJ mol-1, considerably higher than that reported previously for the corresponding Ln(DOTA)- complexes (DOTA is the tetraacetate analog of DOTP). Lanthanide-induced shifts are reported for all 1H, 13C, and 31P nuclei in 11 Ln(DOTP)5- complexes. The proton spectra of these complexes display unusually large lanthanide-induced shifts, one showing a spectrum in which the 1H resonances span 900 ppm. The contact and pseudocontact contributions to these shifts were separated using Reilley's temperature-independent method and the resulting pseudocontact lanthanide-induced NMR shifts were in excellent agreement with those calculated for a structure derived using MMX molecular modeling methods. The pseudocontact shifts provide evidence for Ln (DOTP)5- chelates which have virtually identical structures along the lanthanide series, with the possible exception of Tm(DOTP)5-.
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U2 - 10.1016/0022-2364(92)90314-W
DO - 10.1016/0022-2364(92)90314-W
M3 - Article
AN - SCOPUS:0000605313
SN - 0022-2364
VL - 97
SP - 290
EP - 304
JO - Journal of Magnetic Resonance (1969)
JF - Journal of Magnetic Resonance (1969)
IS - 2
ER -