C6800 Multinuclear NMR Spectroscopy

Faculty of Science
Spring 2020
Extent and Intensity
2/0/0. 2 credit(s) (fasci plus compl plus > 4). Recommended Type of Completion: zk (examination). Other types of completion: k (colloquium).
Teacher(s)
prof. RNDr. Jiří Pinkas, Ph.D. (lecturer)
Guaranteed by
prof. RNDr. Jiří Pinkas, Ph.D.
Department of Chemistry – Chemistry Section – Faculty of Science
Contact Person: prof. RNDr. Jiří Pinkas, Ph.D.
Supplier department: Department of Chemistry – Chemistry Section – Faculty of Science
Timetable
Tue 8:00–9:50 C12/311
Prerequisites
Basic knowledge of general chemistry with emphasis on chemical bonding, structure and symmetry of molecules, and proton and 13C NMR spectroscopy.
Course Enrolment Limitations
The course is also offered to the students of the fields other than those the course is directly associated with.
fields of study / plans the course is directly associated with
there are 28 fields of study the course is directly associated with, display
Course objectives
Basic observables of the NMR spectra, such as shielding constants and chemical shifts, scalar couplings, and relaxation times, are discussed in this course. Influence of chemical and physical factors, structural parameters, and effects of chemical exchange on their values are emphasized. Practical examples and problems are shown from the area of multinuclear NMR spectroscopy of inorganic compounds.

Learning outcomes
Students will learn in this course:
To find symmetry elements in molecules and predict expected number of signals in spectra of the NMR active nuclei present in the molecule.
To estimate the magnitude of chemical shift in spectra of nuclei as a function of molecular structure and electronic environment.
To calculate the expected multiplicity of signals of measured nuclei in interaction with neighbouring active nuclei.
To estimate the magnitude of scalar coupling constants in dependence on bonding parameters and structural features of molecules.
To judge nuclear, electronic, and structural influence on relaxation rates of nuclei.
To establish influence of chemical and physical factors and structural parameters on chemical exchange and its effect on number and shape of signals in NMR spectra.
Syllabus
  • 1. Historical background. Basic concepts: nuclear spin, magnetic moment, magnetogyric ratio, natural abundance, magnetization, population, Larmor frequency.

    2. Shielding constants, diamagnetic and paramagnetic shielding, Ramsey formula. Local and nonlocal effects. Chemical shifts, referencing. Ranges of chemical shifts.

    3. Parameters influencing the magnitude of shielding constant: oxidation state, coordination number, charge, symmetry, HOMO-LUMO gap, electronegativity, normal and inverse halogen series, nephelauxetic and spectrochemical series.

    4. Correlation of chemical shifts with bond lengths and angles, UV maxima, IR force constants, Hammet sigma constants.

    5. Chemical shift effects: isotope effects, SIIS, magnetic anisotropy of chemical groups, temperature, solvent, ASIS.

    6. Satellite signals, isotopomers, abundance calculations.

    7. Chemical equivalence and molecular symmetry. Prochiral and C2 groups. Homotopic, enantiotopic, diastereotopic, and heterotopic nuclei. Chiral solvents, shift reagents.

    8. Dipolar coupling. Solid state NMR spectroscopy.

    9. Scalar coupling. Coupling constants, Dirac model, Pople-Santry formula, reduced coupling constant. Coupling constant effects: s-character, hybridization, electronegativity, coordination number, bond angles, dihedral angles, Karplus equation.

    10. Multiplet construction. Spin system notation. Simple spin systems: AB, ABX, AA'X, AA'XX'. Spectral simulation.

    11. Relaxation. Relaxation times T1 a T2. Correlation time. Extreme narrowing limit. Inversion Recovery and Spin Echo methods.

    12. Relaxation mechanisms: dipolar, chemical shift anisotropy, spin rotation, scalar, quadrupolar, paramagnetic. NOE.

    13. Dynamic NMR spectroscopy. Chemical exchange. Degenerate and nondegenerate systems. Dynamic NMR spectra simulation.

Literature
  • NMR and the periodic table. Edited by Robin Kingsley Harris - Brian E. Mann. London: Academic Press, 1978, 459 s. ISBN 0123276500. info
  • MACOMBER, Roger. A complete introduction to modern NMR spectroscopy. New York, USA: John Wiley and Sons, 1998, 382 pp. ISBN 0471157368. info
  • FRIEBOLIN, Horst. Basic one- and two-dimensional NMR spectroscopy. 3rd ed. Weinheim: Wiley-VCH, 1998, 385 pp. ISBN 3527295135. info
  • BRAUN, Siegmar, Hans - Otto KALINOWSKI and Stefan BERGER. 150 and more basic NMR experiments :a practical course. 2nd exp. ed. Weinheim: Wiley-VCH, 1998, 595 s. ISBN 3-527-29512-7. info
  • Two-dimensional NMR spectroscopy :applications for chemists and biochemists. Edited by William R. Croasmun - Robert M. K. Carlson. 2nd ed. New York: VCH Publishers, 1994, xxii, 958. ISBN 1-56081-664-3. info
  • SANDERS, Jeremy K. M. Modern NMR spectroscopy : a workbook of chemical problems. 2nd ed. Oxford: Oxford University Press, 1993, 127 s. ISBN 0198558120. info
  • BREITMAIER, Eberhard. Structure elucidation by NMR in organic chemistry : a practical guide. Translated by Julia Wade. Chichester: John Wiley & Sons, 1993, 265 s. ISBN 0471933813. info
  • HÁJEK, Milan. Kvantitativní FT NMR spektroskopie v chemické praxi. 1. vyd. Praha: Academia, 1989, 164 s. ISBN 8020000968. URL info
  • SCHRAML, Jan. Dvourozměrná NMR spektroskopie. 1. vyd. Praha: Academia, 1987, 130 s. info
  • DEROME, Andrew E. Modern NMR techniques for chemistry research. Oxford: Pergamon, 1987, xvii, 280. ISBN 0-08-032513-0. info
  • GOLJER, Igor and Tibor LIPTAJ. Nové metódy FT NMR spektroskopie kvapalín. 1. vyd. Bratislava: VEDA vydavatel'stvo Slovenskej akadémie vied, 1986, 181 s. info
  • WEHRLI, F. W. and T. WIRTHLIN. Interpretation of carbon-13 NMR spectra. London: Heyden, 1980, 310 s. ISBN 0-85501-207-2. info
  • FARRAR, Thomas C. and Edwin D. BECKER. Pulse and Fourier Transform NMR : Introduction to Theory and Methods. New York: Academic Press, 1971, 115 s. info
Teaching methods
The course consists of 14 lectures of 50 minutes each. Course materials, such as lecture slides, supplementary articles, tables, are available to students in the Information System of Masaryk University. Additional relevant lectures given by visiting professors under INNOLEC program are part of the course in particular cases.
Assessment methods
There are 3 graded homeworks during the semester. At the end of the course every student will give a short presentation on a selected topic concerning NMR spectroscopy. Written final exam worth 100 pts, minimum 50 pts to pass. Grading weights: final test 75%, homeworks 15%, presentation 10%.
Language of instruction
Czech
Follow-Up Courses
Further comments (probably available only in Czech)
Study Materials
The course can also be completed outside the examination period.
The course is taught annually.
Teacher's information
http://nmr.sci.muni.cz/
The course is also listed under the following terms Spring 2008 - for the purpose of the accreditation, Spring 2011 - only for the accreditation, Spring 2000, Spring 2001, Spring 2002, Spring 2004, Spring 2005, Spring 2006, Spring 2007, Spring 2008, Spring 2009, Spring 2010, Spring 2011, spring 2012 - acreditation, Spring 2013, Spring 2014, Spring 2015, Spring 2016, Spring 2017, spring 2018, Spring 2021, Spring 2022, Spring 2023, Spring 2024, Spring 2025.
  • Enrolment Statistics (Spring 2020, recent)
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