What is NMR?

Nuclear magnetic resonance: Nuclear magnetic resonance spectroscopy is the use of the NMR phenomenon to study physical, chemical, and biological properties of matter. A preeminent technique for determining the structure of organic compounds. Nuclear magnetic resonance is a phenomenon which occurs when the nuclei of certain atoms are immersed in a static magnetic field and exposed to a second oscillating magnetic field. Some nuclei experience this phenomenon, and others do not, dependent upon whether they possess a property called spin. Of all the spectroscopic techniques, this is only technique with which complete analysis and interpretation is expected. NMR is non-destructive technique unlike to mass spectroscopy. Samples weighing less than a milligram can be analyzed efficiently. These techniques are replacing x-ray crystallography for the determination of protein structure. BASICS:
SPIN: Spin is a fundamental property of nature like electrical charge or mass. Spin comes in multiples of 1/2 and can be + or -. Protons, electrons, and neutrons possess spin. Individual unpaired electrons, protons, and neutrons each possess a spin of 1/2. Spin types: The nuclei of many elemental isotopes have a characteristic spin (i) Some nuclei have integral spins (e.g. I = 1, 2, 3 ....), some have fractional spins (e.g. I = 1/2, 3/2, 5/2 ....), (ii) Few have no spin, I = 0 (e.g. 12C, 16O, 32S,). (iii) Isotopes of particular interest and use to organic chemists are 1H, 13C, 19F and 31P, all of which have I = 1/2.

PROPERTIES In nuclear magnetic resonance, it is unpaired nuclear spins that are of importance. When placed in a magnetic field of strength B, a particle with a net spin can absorb a photon, of frequency . The frequency depends on the gyromagnetic ratio, of the particle. =B For hydrogen, = 42.58 MHz / T.

PRINCIPLES OF NMR. The nuclei of all elements carry a charge. When the spins of the protons and neutrons comprising these nuclei are not paired, the overall spin of the charged nucleus generates a magnetic dipole along the spin axis, and the intrinsic magnitude of this dipole is a fundamental nuclear property called the nuclear magnetic moment, . The symmetry of the charge distribution in the nucleus is a function of its internal structure and if this is spherical (i.e. analogous to the symmetry of a 1s hydrogen orbital), it is said to have a corresponding spin angular momentum number of I=1/2, of which examples are 1H, 13C, 15N, 19F, 31P etc. In quantum mechanical terms, the nuclear magnetic moment of a nucleus can align with an externally applied magnetic field of strength Bo in only 2I+1 ways, either re-inforcing or opposing Bo. Lower spin state: The energetically preferred orientation has the magnetic moment aligned parallel with the applied field (spin +1/2) and is often given the notation (a).

Higher spin state: The higher energy anti-parallel orientation (spin -1/2) is referred to as (). The rotational axis of the spinning nucleus cannot be orientated exactly parallel (or anti-parallel) with the direction of the applied field Bo (defined in our coordinate system as about the z axis) but must precess about this field at an angle (for protons about 54) with an angular velocity given by the expression; wo = Bo ...(1) (the Larmor frequency, in Hz) The constant is called the magnetogyric ratio and relates the magnetic moment m and the spin number I for any specific nucleus; = 2pm/hI ...(2) (h is Planck's constant) FLIPPING: The transition of nuclei from one energy state to other energy state is called as FLIPPING. When a proton precess in the aligned aligned orientation, It can pass into opposed orientation by absorbing energy. From opposed orientation (high energy, I=-1/2) it comes back to low energy state (more stable,I==1/2) by losing energy. NUCLEAR RESONANCE The energy required to bring about transition (E=h) or to flip the proton depends upon the strength of external field. Stronger the field greater will be the tendency of nuclei to remain aligned parallel to it. Higher will be the frequency of radiation needed to flip the proton to higher energy state. = H0/2

 = frequency in cycles per sec. H0= Strength of magnetic field in guass. = Gyromagnetic ratio. The energy required to cause flipping corresponds to electromagnetic radiation of frequency 60 million cycles per sec. When we irradiate the precessing nuclei with a beam of electromagnetic radiation of desired frequency, then the low energy nuclei will absorb it and move to higher energy state. The precessing proton will absorb energy from the radio-frequency source only if the precessing frequency is the same as the frequency of the radio frequency beam.i.e. when the quantum energy(h) of electromagnetic radiation matches up the energy difference between the two energy states at the field strength H0.When this occurs, the nucleus and the radio frequency beam are said to be in resonance. Hence, the term nuclear magnetic resonance. It is generally more convenient to to keep the radio frequency constant and strength of the magnetic field is constantly varied. At some value of field strength,the energy required to flip the protons matches the energy of radiation. Absorbtion occurs and a signal is observed. Such a spectrum is called Nuclear magnetic resonance spectrum. Relaxation process: Relaxation process involve some non-radiative transition by which a nucleus in upper transition state returns to lower spin state. Three kinds of relaxation process are: (i) Spin-spin relaxation (ii)Spin-Lattice relaxation (iii)Quadrupole relaxation. Number of signals: The number of signals in the nmr spectrum tell the no. of different sets of equivalent protons in a molecule.

Each signal to a set of equivalent protons. Magnetically equivalent protons are chemically equivalent protons. e.g. (i) Acetone (ii) cyclo-butane (iii) Benzene (iv) Terte methyl methane. (v) Methanol. (vi) Ethyl amine. (vii) Propyl chloride. (viii) 2-Propanol. 1 signal

Position of signals: Position of signals in the spectrum demonstrates the nature of protons viz. aromatic, aliphatic, vinylic,adjacent to some electron withdrawing or electron releasing groups etc. Each of these types of protons will have different electronic environments therefore they absorb at different applied field strength. Cause of chemical shift: When a molecule is placed in a magnetic field, its electrons are caused to circulate and thus, they produce secondary magnetic field called as induced magnetic field. Rotation of electrons about the proton generates a field which opposes the applied field. Thus, the field felt by the proton, is diminished and proton is said to be shielded.

 When induced magnetic field caused by rotation of electrons opposes the applied field at proton, then the proton is said to be shielded. Sheilding shifts the absorbtion upfield to get an effective field strength necessary for absorbtion. When induced magnetic field caused by rotation of electrons reinforce the applied field at proton, then the proton is said to be Deshielded. Desheilding shifts the absorbtion downfield to get an effective field strength necessary for absorbtion. Chemical shifts: Shifts in the positions of nmr (compared with standard reference) absorbtions which arises due to the shielding or deshielding of protons by the electrons are called chemical shifts. Or The difference in the absorbtion position of the proton with respect to TMS (Tetramethyl silane) signal is called as chemical shift. It is denoted by (value). TMS: It is taken as reference /internal standard for measuring the position of 1H, 13C and 29Si in NMR spectroscopy due to following facts: It is chemically inert and miscible with large range of solvents. Its twelve protons are all magnetically equivalent. It is highly volatile and can be easily removed to get back the sample. It does not take part in intermolecular association with the sample. Its resonance position is far away from absorbtions due to protons in most organic molecule. (Delta) chemical shift. Relation:

The value of for a substance with respect to TMS can be obtained by measuring S - TMS where: S = Resonance frequency of sample. TMS = Resonance frequency of TMS. Keeping the radio frequency constant, an nmr signal for a particular set of proton in the sample will appear atdifferent field strength than the signal obtained from TMS. This, the value of S - TMS can be expressed in Guass. Since the operating frequency of the instrument is directly proportional to strength of magnetic field, we can define as: = S - TMS /operating frequency in megacycles per second. is expressed in parts per million. Generally most of the chemical shifts have a range between 0 and 10 Greater the deshielding of protons Factors influencing chemical shift: 1. Inductive effect 2. Vander Waals deshielding 3. Anisotropic effects 4. Hydrogen bonding. 1.Inductive effect A proton is said to be deshielded if it is attached to an electronegative atom or group. Greater the electronegativity of the atom, greater is the deshielding caused to proton. If the deshielding is more for a proton, then its value will also be more. Consider the following compounds: 1. CH3b-CH2a-F 2. CH3b-CH2a-Cl

Two signals are expected for each of the two compounds. Deshielding for protons a in compound (1) is more than that for similar protons in compound (2). As, the distance from the electronegative atom increases, the deshielding effect due to it diminishes. 2. Vander Waals deshielding In overcrowded molecules, it is possible that some protons may be occupying sterically hindered position. Clearly, electron cloud of bulky groups will tend to repel the electron cloud surrounding the proton. Thus, such a proton will be deshielded and will resonate at slightly higher value of delta () than expected in the absence of this effect. 3. Anisotropic effects The deshielding effect on protons attached to C=C is higher than that can be accounted for by the inductive effect alone. Aldehydic and aromatic protons are much more deshielded. Alkyne protons appear at relatively low value of . The value of can in each case can be justified by explaining the manner in which the electron circulate under the influence of applied field. Consider an alkene. It is so oriented that the plane of the double bond is at right angles to applied field. Induced circulation of (pi) electrons generates induced magnetic field which is diamagnetic around carbon atom and paramagnetic in the region of the alkene protons. Thus the protons will feel greater field strength and hence resonance occurs at lower applied field.

4. Hydrogen bonding It has been found that a hydrogen atom exhibiting property of hydrogen bonding in a compound absorbs at a low field in comparison to the one which does not. The hydrogen bonded proton being attached to a highly electronegative atom will have smaller electron density around it. Being Less shielded the field felt by such a proton will be more and hence, resonance will occur downfield. The downfield shift depends upon the strength of hydrogen bonding. Intermolecular and intra-molecular hydrogen bonding can be easily distinguished as the later does not show any shift in absorption due to change in concentration.