Add time:07/29/2019         Source:sciencedirect.com

The Schiff’s base complexes (CO)2(NO)Cr{η5-C5H4C(R) = NNH[2,4-(NO2)2C6H3]} (4 R = H, 5 R = CH3, 6 R = C6H5)) and (CO)3(CH3)M{η5-C5H4C(R) = NNH[2,4-(NO2)2C6H3]} (13, M = Mo, R = H; 14, M = Mo, R = CH3; 17 M = W, R = H; 18 M = W, R = CH3) were obtained from condensation reactions. The structure of 5 was determined by X-ray diffraction studies. The chemical shifts of the C(2)–C(5) carbon atoms of 4–6, 13, 14, 17 and 18 have been assigned using two-dimensional HetCOR NMR spectroscopy. We observed that C(2,5) resonates at a lower field than C(3,4) in 4 and 6, whereas C(3,4) resonates at a lower field than C(2,5) in 5. The correlation between the magnitude of the non-planarity of the Cp-exocyclic carbon to the π-acceptor substituents and the extent of deshielding on C(3,4) of the Cp ring is discussed. The electron density distribution in the cyclopentadienyl ring is discussed on the basis of the 13C NMR data and those of 5 and 14 were compared with calculations using the density functional B3LYP exchange–correlation method.

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