Studies of transition metal phosphine complexes relevant to catalysis

TL;DRAbstract

Methoxycarbonyl compounds of the type [Pd(X)(CO(_2)Me)(L(_2))] (1) and [Pd(X)(CO(_2)Me)(L)(_2)] (2) were used as models in the work related to hydroesterification using methyl formate instead of CO and MeOH. The behaviour of the complexes (1) and (2) in solution was examined, as was their behaviour in the presence of alkenes and nucleophiles. Many of these derivatives were too unstable to isolate, forming the corresponding dichloride complexes [Pd(X)(_2)(L(_2))] (3) and [Pd(X)(_2)(L)(_2)] (4). Several crystal structures of such complexes were obtained. The cationic complex [Pd(CO(_2)Me)(MeCN)(PPh(_3))(_2)](BF(_4)) (5) was synthesised from (2) by removal of the chloride ligand with silver tetrafluoroborate. This is the first isolated cationic methoxycarbonyl complex of palladium. A crystal structure of (5) was obtained. Some of the factors which affected the stability of methoxycarbonyl complexes were examined. Some of these systems were used as precursors for catalytic studies of hydro

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