Introduction ™ The simplest atom, Hydrogen is found in almost all organic compounds that is composed of single proton and single electron, © For purpose of NMR, the key aspect of hydrogen nucleus is its angular momentum properties that resemble classical spinning particle. ® As the spinning hydrogen nucleus is positively charged, it generates magnetic field and possesses a magnetic moment p, just as a charge moving in a “circle. = The NMR experiment exploits the magnetic properties of nuclei to provide information on molecular structure. ony berween Chace moving Spinning aprerioat= The magnetic interaction between the spins of neighboring, non-equivalent NMR-active nuclei may cause splitting of NMR spectrum which is known as spin-spin coupling. ® The splitting pattern is related to the number of equivalent H-atom at the nearby nuclei. Example: 4,1 ,2-tribromoethaneBy examining the structure of 1,1,2-ribromoethane, we might expect only two single peaks that correspond to two different types of hydrogen. However, what ‘we see is slightly different. Instead of two singlet peaks, each peak consists of multiple lines. The signals for H» consists of a doublet that for Hs consists of a triplet. The ‘splitting of the peaks into multiple peaks is called spin-spin coupling which is the direct interaction between the neighboring hydregen nuclei The chemical shift of Ha is affected both by it's own density and also by neighboring hydrogen nuclei Each one of nuclei can spin either one of two ways: spin up (+1/2) or spin down (-1/2). Since there are two Ho nuclei, there are 4 possible spin combination around Ha atom. (tt), (t1), (4t) or (14) Net magnetic field of Ha hydrogen can be modified by each one of the different combination. Two Identical combination sums up to give higher intensity.Pascal triangle & n+1 rule = The Pascal's triangle is a graphical device used to predict the ratio of heights of lines in a split NMR peak. The (n+1) Rule is used to predict the multiplicity and, in conjunction with pascal triangle, splitting pattern of peaks in 'H NMR spectra, states that if a given nucleus is coupled to n number of nuclei, the multiplicity of the peak is n*1Coupling Constant (J) = Spin-Spin coupling causes the spectral lines to split and the distance between two adjacent sub-peaks in split signal is given by coupling constant (J) expressed in Hertz (Hz). = The distance between two peaks for the resonance of one nucleus split by another is a measure of how strongly the nuclear spins influence each other. =/For our doublet in 1,1,2-tribromoethane spectrum, two sub peaks are separated by 6.1 Hz, thus we write 3/.a-b = 6.1 Hz = J value is same regardless of applied magnetic field strength of NMR magnet. This is because the strength of magnetic moment of a neighboring Proton, which is the cause of spin-spin phenomena does not depend on the applied fieldFactors affecting J value The number of bonds intervening between the coupling nuclei is important, since the coupling is transmitted via the electrons of these bonds. ™Geminal coupling invalving protons on —CH2- groups, is strong, 2J being typically 10-18 Hz, but it will only be observed where the gem protons have different chemical ‘shift positions. = Vicinal coupling (three bonds separating the protons) varies from = 0 to 12 Hz in gid systems, but in freely rotating carbon chains (alkyl groups) it is usually around 8 iz. ™Long-range coupling in alkane systems (extending over more than three bonds- i.¢,, 4J and longer) is usually vanishingly small, but is observed within rigid systems. Angle between atom; Trans coupling in alkene groups (3J, 11-19 Hz) is stronger than ¢is coupling (J, -14 Hz).Complex coupling = When a set of hydrogen is coupled to two or more sets of nonequivalent neighbors, the result is a phenomenon called comptex coupling. Example: Methyl acrylate / \\ H.. __ F-0cH, Ome, Hp Ha