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NMR Investigations of Restricted Rotations and Metallotropic Shifts in Rhenium(I) Tricarbonyl Halide Complexes of Pyridyl Carboxamide and Thioamide Ligands

✍ Scribed by Keith G. Orrell; Anthony G. Osborne; Jade O. Prince; Vladimir Šik; Dionyssios K. Vellianitis


Publisher
John Wiley and Sons
Year
2000
Tongue
English
Weight
420 KB
Volume
2000
Category
Article
ISSN
1434-1948

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✦ Synopsis


A series of rhenium(I) tricarbonyl halide complexes of pyridyl 28Ϫ33 kJ mol Ϫ1 . In the pyridyl dicarboxamide and -dithioamide metal chelate complexes metallotropic shifts occur mono-and di-carboxamides and -thioamides has been studied by dynamic NMR techniques. Oxygen coordination between the three donor atoms, O, N, O or S, N, S, energies [∆G ‡ (298.15 K)] being in the range 78Ϫ89 kJ mol Ϫ1 ; these to Re I of the carboxamide ligand reduced the energy barrier to CϪN rotation by 2Ϫ13 kJ mol Ϫ1 whereas sulfurϪRe I high values arise from the strong electron donating properties of the -NR2 (R = Me, Et) groups. coordination of the thioamide ligands led to a reduction of