Palladium(II) chloride complexes PdCl 2L 2 and [PdCl 2L] 2 have been prepared with the phosphine ligands PPh 2CHCH 2 and PPh 2CH 2CHCH 2. The reactions of PdCl 2L 2 complexes with thf·BH 3 afford equilibria in which the components may be identified by 31P{ 1H}-NMR spectroscopy. PdCl 2L 2 and [PdCl 2L] 2 complexes and phosphine–borane adducts are observed. In addition, analogues of the PdCl 2L 2 and [PdCl 2L] 2 complexes are present in which one or both phosphine ligands have undergone alkene hydroboration. The reaction of PdCl 2(PhCN) 2 and the cyclic adduct formed between 9-BBN and PPh 2CH 2CHCH 2 [cyclo-(9-borabicyclo[3.3.1]nonanyl)-propyl(diphenyl)phosphine] has been studied. Opening of the P–B dative bond occurs with the formation of a [PdCl 2L′] 2 complex in which the phosphine ligand contains a pendant borane moiety. Hydrolysis in air yields the crystallographically characterised dimer [PdCl 2(PPh 2CH 2CH 2CH 3)] 2. The X-ray structure of the unsaturated analogue, [PdCl 2(PPh 2CH 2CHCH 2)] 2, has also been obtained. Both compounds exist as symmetrical dimeric structures with terminal and asymmetric bridging halides.