Reactions of phosphites with diols in the presence of N-chlorodiisopropylamine in ether solution led to new compounds formulated as the bicyclic tetraoxyphosphorane, [S(Me(2)C(6)H(2)O)(2)](2)PNMe(2) (1), the hexacoordinated pentaoxyphosphorane, S[(t-Bu)(2)C6H2O]P-2(Me(2)C(3)H(4)O(2))(OCH2CF3) (2), with a P-S interaction indicated by P-31 NMR, and the two phosphates, {(CH3CH2CH2)(CH)[t-Bu)(2)C6H2OH](2)}P-2(O)(OCH2CF3) (3) and S(Me(2)C(6)H(2))(2)(OH)OP(O)(OXyl)(2) (4), resulting from hydrolysis reactions. The X-ray structures of 1 and 4 were obtained, and all were characterized by NMR spectral measurements in solution. Phosphorane 1 possessed a trigonal bipyramidal geometry displaced 29% toward a rectangular pyramid. The lack of PS coordination, potentially available from the two attached eight-membered ring systems, is attributable to strong P-N pi bonding. X-ray analysis shows 4 to form as an acyclic phosphate rather than a cyclic phosphate. This is attributed to the presence of the poor OXyl leaving group. It is proposed that the hydrolysis process leading to acyclic and cyclic phosphates proceeds by way of a hexacoordinated intermediate that forms as a result of PS coordination. Phosphorane 1 crystallizes in the monoclinic space group C2/c with a=26.034(5)Angstrom,b=15.230(2)Angstrom,c=24.687(2)Angstrom,beta=131.31(1)degrees, and Z=8. Phosphate 4 crystallizes in the monoclinic space group P2(1)/c with a=12.971(4)Angstrom,b=22.572(3)Angstrom,c=10.800(2)Angstrom,beta=109.25(2)degrees, and Z=4. The final conventional unweighted residuals are 0.059 (1) and 0.035 (4).