The coordination of Cd2+ with P(CH2OH)(3) (THP) in methanol was followed by P-31 and Cd-111 NMR techniques. A cadmium-to-phosphine coordination ratio of 1:3 has been established, and effective kinetic parameters have been calculated. Air oxidation of THP in the presence of CdCl2 at room temperature produces coordination polymer (3)(infinity)[Cd3Cl6(OP(CH2OH)(3))(2)] (1). The same oxidation reaction at 70 degrees C gives another coordination polymer, (infinity)[CdCl2(OP(CH2OH)(3))] (2). Complexes 1 and 2 are the first structurally characterized complexes featuring OP(CH2OH)(3) as a ligand that acts as a linker between Cd atoms. The addition of NaBPh4 to the reaction mixture gives coordination polymer (infinity)[Na2CdCl2(O2P(CH2OH)(2))(2)(H2O)(3)] (3) with (HOCH2)(2)PO2- as the ligand. Coordination polymers 1-3 have been characterized by X-ray analysis, elemental analysis, and IR spectroscopy.