Phosphorus-palladium complexes, nitrogen ligands

Polar, aprotic solvents such as DMF were necessary for the formation of (126). [Pd(diphos)2] (104) gave the best performance as catalyst. Using [Pd(DBA)2] (105) as palladium source, a number of mono- and bi-dentate nitrogen, phosphorus and arsenic ligands were investigated and Me2PCH2CH2PMe2 was found to be nearly as effective as diphos. The reaction of C02 with a bis(i73-allyl) complex of palladium was believed to be a key step in the process (equation 158). 

Cyclometalation is one of the most reliable and versatile methods for the synthesis of stable Pd-C a-bonds. In this reaction, a palladium (or other metal) complex is reacted with a ligand possessing a donor atom. The metal is directed by the donor atom to insert into a C-H bond, forming a chelate ring. This donor is usually the nitrogen of a tertiary amine, heterocyclic amine, or imine, or a phosphorus in a tertiary phosphine or phosphite. Other donor atoms, such as O and S, are occasionally encountered. The chelate ring size is normally five. ... 

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