Influence of geometric and electronic features of pyridine derivatives and triethylamine on the formation of a metal carboxylate core in reactions producing cadmium( ii) pivalate complexes.

The reaction products of [Cd(piv)] (piv is-OCBu) with isoquinoline (iqn), 2,4-lutidine (lut), phenanthridine (phend), 2,3-cyclododecenopyridine (cpy), and triethylamine (EtN) were synthesized and their structures were determined. The steric factors were found to play a more important role in cadmium( ii) pivalate complexes compared to 3d metal carboxylates in the +2 oxidation state. The reaction of [Cd(piv)] with isoquinoline produces only the mononuclear complex [Cd(piv)(iqn)] ( 1). The reaction of [Cd(piv)] with pyridine derivatives bearing a bulky substituent at the α position is accompanied by the formation of symmetrical dinuclear complexes of the composition [Cd(piv)(L)]. In the complexes with L = lut ( 2) or phend ( 3), the cadmium( ii) atoms are linked by two chelating-bridging carboxylate groups; in the complex with L = cpy ( 4), by four bidentate-bridging groups. The reaction of [Cd(piv)] with EtN in a solution of MeCN gives the centrosymmetric linear trinuclear complex [Cd(piv)(EtN)] ( 6); in a mixture of benzene and hexane, the ionic compound (HEtN)[Cd(piv)(HO)] ( 7). The crystal structures of all synthesized compounds were determined by X-ray diffraction. [ABSTRACT FROM AUTHOR]