2- picolinamide complexes

Copper(JI) has been found to inhibit the hydrolysis of glycylglycine in basic solution (pH> 11).127 Conley and Martin128 have also found that, at pH values in excess of 11, copper(II) inhibits the hydrolysis of glycinamide due to amide hydrogen ionization. Similar results were obtained with picolinamide, and a bis-picolinamide complex of nickel(II) containing deprotonated amide groups was isolated.128... 

Fueled by the success of the Mn (salen) catalysts, new forays have been launched into the realm of hybrid catalyst systems. For example, the Mn-picolinamide-salicylidene complexes (i.e., 13) represent novel oxidation-resistant catalysts which exhibit higher turnover rates than the corresponding Jacobsen-type catalysts. These hybrids are particularly well-suited to the low-cost-but relatively aggressive-oxidant systems, such as bleach. In fact, the epoxidation of trans-P-methylstyrene (14) in the presence of 5 mol% of catalyst 13 and an excess of sodium hypochlorite proceeds with an ee of 53%. Understanding of the mechanistic aspects of these catalysts is complicated by their lack of C2 symmetry. For example, it is not yet clear whether the 5-membered or 6-membered metallocycle plays the decisive role in enantioselectivity however, in any event, the active form is believed to be a manganese 0x0 complex <96TL2725>. 

A variety of gold(III) complexes of carboxamido substituted heterocyclic ligands are obtained by reaction of [AuCh] with the appropriate ligands, these include [Au (N,N )Cl2j (HN,N =picolinamide) (IS) [70], [Au(N,N, N")Cl]Cl [N,N H,N" = N-(8-quinolyl)pyridine-2-carboxamide (16), N-(8-quinolyl)glycine-2-carboxamide (17) or N-(8-quinolyl)-L-alanine-2-carboxamide (18)] [71] (Figure 2.11). 

Complexes of picolinamide with lanthanide perchlorates, nitrates, and isothiocyanates have been isolated by Condorelli et al. (59). All these complexes show changes in the stoichiometry on going from La(III) to Lu(III). The ligand acts as bi-dentate with the oxygen of the amide group as well as the heterocyclic nitrogen coordinating to the metal (Structure I). While the anions in the perchlorate complexes are not coordinated to lanthanide ions, those in the nitrate and isothiocyanate complexes are coordinated. 

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