Allyl Complexes by Nucleophilic Attack

Compound la is prepared by reacting bis(benzonitrile)palladium chloride with butadiene in benzeneTHF or acetone - at RT. In methanol, the methoxy complex Ib is formed instead , and in acetic acid the acetate Ic is produced . Additional examples of nucleophiles are sulfinates and amines. The E groups are readily displaced e.g., CH3O, acetate and (CH3)2N can be rapidly displaced in the presence of catalytic amounts of acid. 

The alcoxy complexes Ib are best prepared by reacting the diene and [PdClJ at RT in alcohol . Different alcohols and dienes may be used, e.g., isoprene, 4-methyl-1,3-pentadiene, 2,3-dimethylbutadiene and various cyclic dienes .  

The acetoxy complexes Ic have been prepared either using [PdCl] in refluxing acetic acid or with palladium acetate at RT . Amino complexes are preferably prepared in THF or acetone and are labile . However, using diisopropylamine, a complex Ig may be isolated.  

In the stable methoxy- and acetoxy complexes Ib and Ic the bridging chloride may be exchanged for other groups, e.g., acetate, thiocyanate, acetoacetate and cyclopentadienyl 1 . 

Formation of Carbon-Transition and Inner Transition Metal Bond 5.8.2.4. from Conjugated Dienes 

---