title: Chelation of vanadium(V) by difluoromethylene bisphosphonate, a structural analogue of pyrophosphate.
abstract: The structural and functional analogy between difluoromethylene bisphosphonate (CF2PP) and pyrophosphate (PPi) is investigated in a reaction with V(V) in the form of vanadate. The reaction of CF2PP with vanadate was investigated using 1.00 M KCl as supporting electrolyte over the ranges 3 < or = [CF2PP] < or = 60 mM and 2.06 < or = pH < or = 11.80. 51V, 19F, and 31P NMR spectroscopic studies showed that a 1:1 species was formed with an H+-dependent formation constant of 110 M-1 at pH 7.22. Results of solution experiments and ab initio calculations are consistent with CF2PP coordinating V(V) in a bidentate manner, as previously reported for PPi. Below pH 4, a minor complex forms, which is consistent with a 1:2 stoichiometry. This complex was also observed with pyrophosphate. The X-ray crystal structure of the monoprotonated difluoromethylene bisphosphonate anion (H[CF2PP]3-)-toludine complex is presented. The H[CF2PP]3- anion crystallized in the triclinic space group P with a = 12.7629(7) A, b = 13.3992(7) A, c = 17.1002(9) A, and V = 2584.4(2) A3, and Z = 2. Sheets of the layers of anions are connected through a network of H-bonds and separated by a layer of toludine cations. The structural features are investigated, and the CF2PP anion was found to be longer and wider than the corresponding PPi. Given the larger size of this anion compared to PPi, the chelation affinity upon CF2 substitution was found to be 4-5-fold reduced at neutral pH.
authors.affiliation: Department of Chemistry, Colorado State University, Fort Collins, CO 80523, USA. crans@lamar.colostate.edu
authors.forename: Debbie C
authors.initials: DC
authors.lastname: Crans
authors.forename: Alvin A
authors.initials: AA
authors.lastname: Holder
authors.forename: Tapan Kumar
authors.initials: TK
authors.lastname: Saha
authors.forename: G K Surya
authors.initials: GK
authors.lastname: Prakash
authors.forename: Muhammed
authors.initials: M
authors.lastname: Yousufuddin
authors.forename: Roman
authors.initials: R
authors.lastname: Kultyshev
authors.forename: Rehana
authors.initials: R
authors.lastname: Ismail
authors.forename: Myron F
authors.initials: MF
authors.lastname: Goodman
authors.forename: James
authors.initials: J
authors.lastname: Borden
authors.forename: Jan
authors.initials: J
authors.lastname: Florian
mesh_terms: D000838:Anions; D002614:Chelating Agents / Q000737:chemistry; D002621:Chemistry / Q000379:methods*; D018360:Crystallography, X-Ray; D011756:Diphosphates / Q000737:chemistry* / Q000494:pharmacology; D004164:Diphosphonates / Q000737:chemistry* / Q000494:pharmacology; D004573:Electrolytes; D006859:Hydrogen / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D063065:Organophosphonates / Q000737:chemistry; D012964:Sodium / Q000737:chemistry; D014639:Vanadium / Q000737:chemistry*
chemical_list: D000838:Anions; D002614:Chelating Agents; D011756:Diphosphates; D004164:Diphosphonates; D004573:Electrolytes; D063065:Organophosphonates; D014639:Vanadium; D006859:Hydrogen; D012964:Sodium