The role of ancillary ligands and of electron poor alkenes and alkynes in stabilizing Pd(0) derivatives: A comparative study

The peculiar characteristics of the ligand neocuproine (2,9-dimethylphenanthroline) allow a number of exchange equilibrium studies between the low valence complex [Pd(eta(2)-nq)(Neocup)] (nq = naphthoquinone; Neocup = neocuproine) and several alkenes and alkynes. A new order of stability which compares differently unsaturated molecules was established. An overview of the factors governing the stability of palladium(0) alkene and alkyne derivatives as a function of the steric and electronic characteristics of both the unsaturated molecule and the ligand becomes accessible and a comparison with the previously determined order was therefore feasible. Such a comparison enlightens the importance of the substituent methyl groups in ortho position of the hetero-aromatic ring which represents the molecular fragment common to all the ligands considered. Taking advantage of the steric requirements of the alkene tmetc (tmetc = tetramethylethylenetetracarboxylate) a kinetic investigation of the reaction between the olefin itself and the complexes [Pd(eta(2)-dmfu)(L-L')] (dmfu = dimethylfumarate; L-L' = 8-diphenylphosphanyl-2-methyl-quinoline, neocuproine, phenanthroline) was carried out. The structures of the complexes [Pd(eta(2)-dmfu)(DPPQ)] and [Pd(eta(2)-deta)(Neocup)] (deta = but-2-ynedioc acid diethyl ester) were also reported in the present paper. The structure of the latter represents the first example of a palladium(0) complex in which the N(2)C(2) donor set around the metal centre is supported by a chelating eta(2)-alkyne