Synthesis and coordination chemistry of (carbamoylmethyl)thiophosphonates. Crystal and molecular structure of cis-dioxodichlorobis[diethyl((diethylcarbamoyl)methyl)thiophosphonate]molybdenum(VI)

Bifunctional (carbamoylmethyl)thiophosphonates, (RO)2P(S)CH2C(O)NEt2 (R = Et, Bu), have been prepared and characterized by elemental analysis and mass, infrared, and NMR spectroscopy. The coordination chemistry of one ligand (R = Et) with molybdenyl, lanthanide, and uranyl ions has been surveyed. cis-Dioxodichlorobis[diethyl((diethylcarbamoyl)methyl)thiophosphonated]molybdenum(VI), MoO2Cl2[(C7H5O)2P(S)CH2C(O)N(C2H5)2]2 has been isolated from the combination of MoO2Cl2 and the thiophosphonate ligand in ethanol/ether mixtures. The resulting complex has been characterized by elemental analyses, infrared and 31P and 13C NMR spectroscopy, and single-crystal X-ray diffraction analysis. The crystal parameters are reported. The structure was solved by heavy-atom methods, and blocked least-squares refinements converged at R/sub F/ = 5.6% and R/sub wF/ = 5.9% on 2670 unique reflections with F ≥ 5sigma(F). The structure contains monomeric units of the complex with the six-coordinate Mo atom having a pseudooctohedral coordination geometry. The two (carbamoylmethyl)thiophosphonate ligands are bonded to the Mo atom in a monodentate mode through the carbonyl oxygen atoms. The important bond distances were measured and are reported. 29 references, 1 figure, 3 tables