Inorganic Coordination Polymers. Ix. Titanium (Iv) Phosphinate Polymers

摘要

The following titanium(IV) phosphinates were prepared, mainly by metathesis: (i) Ti(OR'')2(OPRR'O)2 with R, R', and R'', respectively, CH3, CH3, or C4H9; CH3, C6H5, and C2H5; or C6H5, C6H5, and C2H5 or i-C3H7; (ii) TiCl2(OP(C6H5)2O)2; (iii) TiO(OPRR'O)2 with R and R' both CH3, both C6H5, or one CH3 and one C6H5; (iv) Ti(OP(C6H5)2O)4; and (v) Ti(BB) (OPRR'O)2 with BB, R, and R', respectively, ortho-OPhO, CH3 or C6H5, and C6H5; ortho-OPhCO2, CH3, and C6H5; (CH3)2C(O-)CH2CH(O-)CH3, C6H5, and C6H5; OC3H6O, CH3 or C6H5, and C6H5 P(O)2CH2P(O)2C6H5, CH3, and C6H5. TiCl2(OP(C6H5)2O)2 was prepared by the thermal decomposition of TiCl4(OP(C6H5)2OC2H5)2. Molecular weight data show that all the titanium(IV) phosphinates made are at least trimers, and that some have degrees of polymerization exceeding 20. Their infrared spectra are consistent with phosphinate bridging, and it is probable that double phosphinate bridges are present in most of the polymers. Infrared data also are in accord with Ti(O) analysis shows that weight loss starts at temperatures as high as 450 deg in nitrogen for some of the polymers prepared. (Author)