Iodine NMR Introduction (127I)
Contents

 

 

1. General Information

Atomic Weight126.904473
Natural Abundance, %100
Spin5/2
Gyromagnetic Ratio,
rad/(Tl*s)		5.3525 107
Quadrupole Moment, m2-0.79 10-28
Frequency (1H=100MHz), MHz   20.007
Receptivity (13C=1.00)530
Sensitivity (1H=1.00)9.34 10-2
ReferenceNaI (aq)

 

An example of 127I Spectrum

127I spectrum example
Selected Parameters
SF= 40.04MHz
SW=100000Hz
SR=27895.5
SI=64K
O1=35000
AQ=0.0051
RD=0
PW=30
NS=16384
TE=297K
Sample Info
Nucleus: 127I
Solvent: D2O
Sample: 5M NaI
Hardware: Bruker AC200

 

 

2. Experimental examples

   Due to large quadrupole moment of iodine high-resolution spectra can not be obtained for covalent compounds. Most investigations were done on highly symmetric ions, such as I- or IO4-, and were destined to kinetics and equilibrium constants measurements, to examine solvation processes and to study anion binding to large molecules. It is the sensitivity of qudrupolar relaxation to molecular and ionic surrounding, that made it possible to obtain a detailed insight into ion-ion pairing processes involving iodide anions. In some cases quadrupole relaxation has become a very useful method for the study of I- interactions with other molecules.

 

0.5M NaI. 127I spectrum I(-) ion in water
0.5M NaI in D2O; 127I Spectrum
DV1/2=2200Hz d=0ppm		 I- ion solvated by water molecules.

 

 

5M NaI. 127I spectrum Na--I ion pair in water
5M NaI in D2O; 127I Spectrum
DV1/2=3200Hz d=45ppm		 I- - Na+ ion pair solvated by water molecules.
   Increasing NaI concentration leads to the ion pair formation and linebroadening in the spectrum.

 

  High-resolution 127I spectra also were recorded for tetrahedral IO4- ion(see references below).

 

0.5M NaIO4. 127I spectrum IO4(-) structure
0.5M NaIO4 in D2O; 127I Spectrum
DV1/2=1000Hz d=4110ppm
                               		The structure of IO4- ion.
  Click here to see ab-initio optimized IO4- structure in 3D VRML format.

 

 

Download Spectra and Pictures

 

 

3. Coupling constants, chemical shift range and relaxation

Coupling Constants
J1Compound Value, Hz reference
19F-127IIF6+27302.7
19F-127IIF721002.8, 2.9
13C-127ICH3I< 602.10
17O-127IIO4-4892.6
129Sn-127I  SnI49402.11
129Sn-127ISnClI310972.12
129Sn-127ISnCl3I16382.12

 

Chemical Shift Range(picture from ref. 1.2):
0ppm(I-/H2O) - 4000ppm (IO4-)

chenical shifts range picture

 

Relaxation
covalentionic
T1, s below 10-7below 5 10-4

 

 

4.Molecules and Systems studied by 127I NMR

 

Molecules/Systems Methods and Comments Reference
HI127I NMR in solution2.1
I2 + I- = I3-127I NMR in solution2.2
Horseradish peroxidase + I-127I NMR in solution2.3
Poly-N-vinylamides + I-127I NMR in solution2.4
Polyvinylpyrrolidone + I-127I NMR in solution2.5
IO4-127I NMR in solution2.6
(n-C4H9)4NIO4
(n-C4H9)4PIO4		127I Solid State NMR3.1
(CH3)4AsIO4127I Solid State NMR3.2
CuI127I magic-angle spinning NMR 3.3
KIcrystall127I Solid State NMR3.4
(CH3)3C2H5NI127I Solid State NMR3.5

 

 

5. References

Books

 

1.1 Author:
   Akitt, J.W.
Title:
   The Quadrupolar Halides Chlorine, Bromine and Iodine
Reference:
   In: Multinuclear NMR, ed. J. Mason, Plenum, New York, 1987

1.2 Author:
   Brevard, C. and Granger, P.
Title:
  Handbook of High Resolution Multinuclear NMR
Reference:
   John Wiley & Sons, New York, 1981

1.3 Author:
   Lindman, B. and Forsen, S.
Title:
   Chlorine, Bromine and Iodine NMR.
Reference:
   In: NMR- Basic Principles and Progress. Grundlagen und Fortschritte, Eds. P. Diehl, E. Fluck, R. Kosfeld, Springer Verlag, Berlin, Vol. 12, 1976



127I NMR in Solution

2.1 Author:
   Masuda Y. and Kanda T.
Reference:
   J.Phys.Soc.Jpn., 1954, 9, 82.

2.2 Author:
   Myers O.E.
Reference:
   J.Chem.Phys. 1958, 28, 1027.

2.3 Author:
   Sakurada, Junji; Hosoya, Toichiro; Shimizu, Toru; Hatano, Masahiro
Reference:
   Journal, CMLTAG, Chem.Lett., EN, 1985, 211-214
Title:
   127I Nuclear Magnetic Resonance Studies On The Interaction Of Iodide Ion With Horseradish Peroxidase
With abstract

2.4 Author:
   Yakimov, S. A.; Kirsh, Yu. E.; Sibel'dina, L. A.
Reference:
   Journal, RJPCAR, Russ.J.Phys.Chem.(Engl.Transl.), EN, 61, 12, 1987, 1764-1766
Title:
   The Interaction of Poly-N-vinylamides with Iodide in Water
With abstract

2.5 Author:
   Kirsh, Yu. E.; Yakimov, S. A.; Sibel'dina, L. A.; Karaputadze, T. M.
Reference:
   Journal, RJPCAR, Russ.J.Phys.Chem.(Engl.Transl.), EN, 62, 2, 1988, 152-154
Title:
   Interaction of Polyvinylpyrrolidone with the Ions of Inorganic Salts in Aqueous Solution
With abstract

2.6 Author:
   Dove, Michael F. A.; Sanders, Jeremy C. P.; Appelman, Evan H.
Reference:
   Journal, MRCHEG, Magn.Reson.Chem., EN, 33, 1, 1995, 44-58
Title:
   Comparative Multinuclear (35Cl, 79Br, 81Br, 127I and 17O) Magnetic Resonance Study of the Perhalate Anions XO4(-) (X = Cl, Br or I) in Acetonitrile Solution
With abstract

2.7 Author:
    Brownstein, M., Selig, H.
Reference:
   Inorg. Chem. 1972, 11, 656
Title:
   A spectroscopic Study of IF7 and IF6(+) in Anhydrous Hydrogen Fluoride

2.8 Author:
    Gillespie, R.J., Quail, J.W.
Reference:
   Can. J.Chem. 1964, 42, 2671
Title:
   The 19F N.M.R. Spectrum of IF7

2.9 Author:
    Muetterties, E.L., Packer, K.J.
Reference:
   J. Am. Chem. Soc.1964, 86, 293
Title:
   Intramolecular Ligand Exchange in Seven-Coordinate Structures

2.10 Author:
    Farrar, T.C., Druck, S.J., Shoup R.R., Becker, E.D.
Reference:
   J. Am. Chem. Soc. 1972, 94, 699
Title:
   Temperature-Dependent 13C Relaxation Studies of Small Molecules

2.11 Author:
    Sharp, R.R.
Reference:
   J. Chem. Phys. 1972, 57, 5321
Title:
   Rotational Diffusion and Magnetic Relaxation of 119Sn in Liquid SnCl4 and SnI4

2.12 Author:
    Sharp, R.R., Tolan J.W.
Reference:
   J. Chem. Phys. 1976, 65, 522
Title:
   Nuclear magnetic relaxation of 119Sn, 35Cl, and 127I in two Symmetric Top Molecules SnCl3I and SnI3Cl, in liquid mixtures


127I NMR in Solid State

3.1 Author:
   Burkert, Paul K.; Grommelt, M.
Reference:
   Journal, ZNBSEN, Z.Naturforsch.B, GE, 43, 11, 1988, 1381-1385
Title:
   127I Solid-State NMR Investigations on (n-C4H9)4NIO4 and (n-C4H9)4PIO4
With abstract

3.2 Author:
   Grommelt, M.; Burkert, P. K.
Reference:
   Journal, ZNBSEN, Z.Naturforsch.B, EN, 44, 9, 1989, 1053-1059
Title:
   127I, 185Re and 187Re Solid State NMR Measurements on (CH3)4AsIO4 and (CH3)4AsReO4
With abstract

3.3 Author:
   Hayasi, Shigenobu; Hayamizu, Kikuko
Reference:
   Journal, JCPSA6, J.Chem.Phys., EN, 92, 5, 1990, 2818-2827
Title:
   Effect of spinning on chemical shifts in magic-angle-spinning nuclear magnetic resonance
With abstract

3.4 Author:
   Lee, Nelson; Sanctuary, B. C.; Halstead, T. K.
Reference:
   Journal, JOMRA4, J.Magn.Reson., EN, 98, 3, 1992, 534-555
Title:
   127I NMR Study of Quadrupolar Echoes in KI
With abstract

3.5 Author:
   Ishida, Hiroyuki; Furukawa, Yoshihiro; Kashino, Setsuo; Sato, Setsuko; Ikeda, Ryuichi
Reference:
   Journal, BBPCAX, Ber.Bunsen-Ges.Phys.Chem., EN, 100, 4, 1996, 433-439
Title:
   Phase Transitions and Ionic Motions in Solid Trimethylethylammonium Iodide Studied by 1H and 127I NMR, Electrical Conductivity, X-ray Diffraction, and Thermal Analysis
With abstract


Zero-field NMR, Relaxation, NQR, etc.

4.1 Author:
   Burkert, Paul K.
Reference:
   Journal, ZNBAD2, Z.Naturforsch.B Anorg.Chem.Org.Chem., GE, 35, 11, 1980, 1349-1354
Title:
   Spectroscopic Investigations in the Solid State Chemistry, XIII Temperature Dependence of the 127I-Nuclear Quadrupole Coupling in NH4IO4 and other Periodates
With abstract

4.2 Author:
   Lee, Carolyn W. B.; Sanctuary, B. C.
Reference:
   Journal, JOMRA4, J.Magn.Reson., EN, 59, 2, 1984, 189-196
Title:
   Multipole NMR. VIII. Evidence for Multipole Echoes for I = 5/2
With abstract

4.3 Author:
   Jarret, Ronald M.; Saunders, Martin
Reference:
   Journal, JACSAT, J.Amer.Chem.Soc., EN, 108, 24, 1986, 7549-7553
Title:
   The Use of various Nuclei as Probes in a New NMR Method for Obtaining Proton/Deuteron Fractionation Data
With abstract

4.4 Author:
   Finter, C. K.; Hertz, H. G.
Reference:
   Journal, ZPCFAX, Z.Phys.Chem.(Munich), EN, 148, 1986, 75-96
Title:
   NMR Relaxation Study of I- and Na+ Solvation Structure in Formamide (FA) and Preferential Solvation of these Ions in the Mixture FA/H2O
With abstract

4.5 Author:
   Finter, C. K.; Hertz, H. G.
Reference:
   Journal, JCPBAN, J.Chim.Phys.Phys.Chim.Biol., EN, 85, 5, 1988, 589-596
Title:
   Nmr Relaxation Study Of I- And Na+ Solvation Structure In Dimethyl Formamide (Dmf)
With abstract

4.6 Author:
   Suezawa, Hiroko; Horiike, Norikazu; Yamazaki, Satomi; Kamachi, Hiroshi; Hirota, Minoru
Reference:
   Journal, JPCHAX, J.Phys.Chem., EN, 95, 26, 1991, 10787-10796
Title:
   Multinuclear NMR Spectroscopic Studies on Ionic Interactions. Interactions between Nitrogen Cations and Halide Ions
With abstract

4.7 Author:
   Kehrer, Armin; Weiden, Norbert; Weiss, Alarich
Reference:
   Journal, ZPCFAX, Z.Phys.Chem.(Munich), EN, 178, 1, 1992, 1-24
Title:
   The Electric Field Gradient at the Bromine and Deuteron Sites in Deuterated Glycyl-L-alanine Hydrobromide Monohydrate and the Iodine Site in Glycyl-L-alanine Hydroiodide Monohydrate. A Single Ctystal NMR/NQR Study
With abstract

4.8 Author:
   Roberts, James E.; Schnitker, Jurgen
Reference:
   Journal, JPCHAX, J.Phys.Chem., EN, 97, 20, 1993, 5410-5417
Title:
   Ionic Quadrupolar Relaxation in Aqueous Solution: Dynamics of the Hydration Sphere
With abstract

4.9 Author:
   Aliev, Abil E.; Harris, Kenneth D. M.; Barrie, Patrick J.; Camus, Stephanie
Reference:
   Journal, JCFTEV, J.Chem.Soc.Faraday Trans., EN, 90, 24, 1994, 3729-3730
Title:
   Carbon-Halogen Second-order Quadrupolar and Indirect Spin-Spin Coupling Effects in High-resolution Solid-state 13C NMR Spectra of Halobenzenes
With abstract

4.10 Author:
   Olender, Z.; Poupko, R.; Luz, Z.; Tesche, B.; Zimmermann, H.; Haeberlen, U.
Reference:
   Journal, JMRAE2, J.Magn.Reson.Ser.A, EN, 114, 2, 1995, 179-187
Title:
   Carbon-13 Chemical-Shift Tensors and Relaxation Phenomena in Solid Trimethylsulfoxonium Iodide. A Single-Crystal NMR Study
With abstract

4.11 Author:
   Liao, Ming-Yuan; Templin, Raymond; Harbison, Gerard S.
Reference:
   Journal, JACSAT, J.Amer.Chem.Soc., EN, 117, 37, 1995, 9535-9541
Title:
   Discrete Secondary Isotope Effects in Zero-Field NMR: Their Relationship to Halide Ion Coordination
With abstract


Related articles

5.1 I-/I3- Equilibrium constant has been measured independently, see for example:
Author:
   Stiopyn, B.D., Pliusheev, V.E.,Fakeev, A.A.
Reference:
   Uspekhi Khimii(Rus.) XXXIV, 11, 1965, p.1881
Title:
   Alkali Metals and Ammonium halogenates

5.2 The structures of I3- and I5- anions have been determined by X-ray analisys, see for example (and references there):
Author:
   Hach, R.J. and Rundle, R.E.
Reference:
   J. Am. Chem. Soc., 73, 1951, p.4321
Title:
   The structure of Tetramethylammonium Pentaiodide



The appropriate reference to this article:
Ananikov V.P., "Iodine NMR Introduction (127I)", 1997; http://nmr.ioc.ac.ru/val/127i-nmr/127i.htm

(c) Ananikov V.P. September 1997

Valentin P. Ananikov
NMR Laboratory
N.D. Zelinsky Institute of Organic Chemistry
http://nmr.ioc.ac.ru/Staff/AnanikovVP/