SYNTHESIS AND PROPERTIES OF AMIDOPALLADIUM(II) AND ALKOXOPALLADIUM(II) COMPLEXES WITH TMEDA (N,N,N',N'-TETRAMETHYLETHYLENEDIAMINE) LIGAND

PdCl2(tmeda) reacts with NaN(SiMe(3))(2) to give PdCl[N(SiMe(3))(2)](tmeda) (1). Single crystal X-ray analysis shows the structure of 1 which has a slightly distorted square planar coordination around the Pd center with Pd-N(amido) bond distance of 2.043(6) Angstrom and Pd-N(amine) bond distances of 2.104(7) and 2.102(7) Angstrom, respectively. Reactions of complex 1 with 1,1,1,3,3,3-hexafluoro-2-propanol and with phenol cause substitution of the amido ligand to give the corresponding alkoxide and phenoxide palladium complexes, PdCl(OR)(tmeda) (2: R=CH(CF3)(2), 3: R=C6H5, respectively). Reactions of dimethylpalladium complex, PdMe(2)(tmeda), with the fluoro alcohol and with phenol give PdMe(OCH(CF3)(2))(tmeda) (4) and PdMe(OC6H5)(tmeda) (5), respectively. Complex 5 reacts further with HOPh to give PdMe(OC6H5)(tmeda).(HOPh) (6) whose H-1 NMR spectrum shows the OH hydrogen peak at extremely low magnetic field position (10.3 ppm) due to strong O-H...O hydrogen bonding between the phenoxide ligand and phenol. The tmeda ligand in complex 4 is easily displaced by addition of phosphine ligands such as dppm (bis(diphenylphosphino)methane), dppe (1,2-bis(diphenylphosphino)ethane), and dppp (1, 3-bis(diphenylphosphino)propane) to give the corresponding palladium alkoxide complexes with the phosphine ligand, PdMe(OCH(CF3)(2))(L) (7: L = dppm; 8: L = dppe; 9: L = dppp).