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Primary and secondary binding sites for lanthanide shift reagents with amides. Differential behavior of cis vs trans amide isomers with LSR

✍ Scribed by Laurine Laplanche Graham


Book ID
102951746
Publisher
John Wiley and Sons
Year
1980
Tongue
English
Weight
526 KB
Volume
14
Category
Article
ISSN
0749-1581

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✦ Synopsis


Lanthanide induced shifts (LIS) were measured for four dimethylamides, RCON(CH,),, and four monomethyl amides, RCONHCH,, R = H, CH,, CF, and CCl,, using Eu(fod), in c a and benzene (c6D6) solution. Structural correlations for HCON(CH,), and CH,CON(CH,)2 in both solvents yield a preferred binding site for the Eu(fod), on one of the lone-pair orbitals of the oxygen atom, with a probable site of secondary importance on the other lone-pair orbital. The cis vs trans isomers of HCONHCH, and CH,CONHCH, exhibit remarkably different chemical shift behavior upon addition of Eu(fod),.