chemical shift 化学位移课件精品.pptVIP

Chemical Shift ω=γB0 For a same kind of nucleus, the ?0 should be the same! The magnetic field felt by the nucleus is not the same as applied field The e- cloud that surrounds the nucleus has motion and generates a magnetic moment. This magnetic field alters B0 in the micro-environment around the nucleus This electronic modulation of the B0 field is called magnetic shielding, ? B = B0(1 - ?) Chemical Shift Magnetic field at the nuclei is NOT equal to the applied field because of shielding or deshielding of electrons around the nuclei. Variation of the resonance frequency with shielding is called the chemical shift Example Inductive Effects Inductive Effects Anisotropic Effects Anisotropic Effects Anisotropic Effects * * * Chemical Shift B=B0(1-?)=B0- Bloc ?=?B0(1-?) HO-CH2-CH3 wo low field high field Example ethanol Chemical Shift Scale ω=γB0 ν=B0(1-?)γ/2π △ν=B0(?1-?2)γ/2π 1）B0 is constant δ=(νS -νR)/νR=(?S-?R) /(1-?R) =(?S-?R) (?R1) 2) ν0 is constant δ=(BS -BR)/BR=(?S-?R) /(1-?R) =(?S-?R) (?R1) δ=(?S-?R) ppm (10-6) Standard References ? = 0 The most common reference compound is tetramethylsilane, TMS TMS is used as reference because it is soluble in most organic solvents, is inert, volatile, and has 12 equivalent 1Hs and 4 equivalent 13Cs. TMS is not water soluble, so can’t be used in aqueous media, then use 2,2-dimethyl-2-silapentane-5-sulfonic acid, DSS (? = 0.015 ppm) Other references can be used, such as the residual solvent peak, dioxane for 13C. Lots of electrons nearby Few electrons nearby Chemical shifts are influenced by the electronic environment. Therefore, they are diagnostic for particular types of molecular structures. The following figure indicates average ranges of proton chemical shifts for different types of molecules. Different functional groups experience different effective field Scales for Different Nuclei .The sh