6-Physical Methods.pptVIP

Synthesis and Characterization For a new organometallic complex, Needs isolation first Air sensitive, especially d-block and f-block elements Schlenk glassware, glove-box Assign its stereochemistry Knows something about its properties Spectroscopic and crystallographic analysis Mainly NMR 1H NMR spectroscopy d -10.44 (d, 2J(P,H) = 15.0 Hz, 1H, Ha) Trans coupling (90-160 Hz)/cis coupling (10-30 Hz) Stereochemistry assignment Figure Virtual coupling (虚假偶合 ) Phosphorus, I = 1/2 PMe3, PMe2Ph Two phosphorus atoms are cis ? a simple doublet for the Me group. When they are trans to each other ? a distorted triplet or virtual triplet. Large P-P coupling ? methyl group couples to its own P and the trans P equally. Figure Diastereotopy Diastereotopic groups No symmetry element of the molecule relates the groups. Resonate at different chemical shifts. Regardless of M—P or C—C bonds are freely rotating Chemical shifts Chemical shift in organometallic compounds are much variable. For example: Free alkene (d 5 -7) Co-ordinated (d 2 – 5) Ir(III) hydride complex Trans to high field ligand e.g. H ? -10 ppm Trans to low field ligand e.g. H2O ? -40 ppm Paramagnetic complexes Large shifts in the NMR resonaces (h6-C6H6)2V at 290 ppm Broadened signals ? may be effectively unobserved. 13C NMR spectroscopy 13C (I =1/2) only 1% of natural carbon Needs longer acquistion time 13C{1H}, proton-decoupled spectrum Off-resonace-decoupled spectrum Only 1-bond C,H couplings Reveals number of H attached to the C CH3, quartet CH2, triplet CH, doublet Coupling is transmitted through s bond, the higher the s character of a bond, the higher is the coupling. For example in C—H sp3 ~ 125 Hz, sp2 ~160 Hz sp ~ 250 Hz 13C NMR Spectrum Characteristic resonance positions Alkyls: – 40 to 20 ppm Alkenes, Cp, arenes: 40 to 120 ppm Terminal C?O: 150 to 220 ppm Bridging C?O: 230 to 290 ppm Carbenes: 200 to 400 ppm 13C NMR Spectrum Relaxation problem e.g. C?O, relaxation reagent, Cr(acac)3