Structure and chelation geometry of α,β,γ-tridentate triammine(dihydrogentriphosphato)cobalt(III), [Co(NH3)3(H2P3O10)]

Merritt, E.A.; Sundaralingam, M.

doi:10.1107/s0567740881006456

Cited by 12 publications

(3 citation statements)

References 5 publications

(7 reference statements)

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“…All other previous work with vanadyl has reported only equatorial phosphate coordination, corresponding to the β- and γ-phosphates of ATP. The proposed structure is consistent, however, with several X-ray crystal structures of other metal complexes with triphosphate (two containing Co(III) [60,61] and one Cd(II) [62]) or ATP (including Mn(II) [63,64], Mg(II), Ca(II) [65], Ni(II) [66], Cu(II) and Zn(II) [67]) as tridentate ligands. An example of one such complex is shown in Figure S8.…”

Section: Discussionsupporting

confidence: 84%

VO²⁺–hydroxyapatite complexes as models for vanadyl coordination to phosphate in bone

2013

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We describe a 1D and 2D ESEEM investigation of VO2+ adsorbed on hydroxyapatite (HA) at different concentrations and compare with VO2+-triphosphate (TPH) complexes studied previously in detail, in an effort to provide more insight into the structure of VO2+coordination in bone. Structures of this interaction are important because of the role of bone in the long-term storage of administered vanadium, and the likely role of bone in the steady-state release of vanadium leading to the chronic insulin-enhancing anti-diabetic effects of vanadyl complexes. Three similar sets of cross-peaks from phosphorus nuclei observed in the 31P HYSCORE spectra of VO2+-HA, VO2+-TPH, and VO2+-bone suggest a common tridentate binding motif for triphosphate moieties to the vanadyl ion. The similarities between the systems present the possibility that in vivo vanadyl coordination in bone is relatively uniform. Experiments with HA samples containing different amounts of adsorbed VO2+ demonstrate additional peculiarities of the ion-adsorbent interaction which can be expected in vivo. HYSCORE spectra of HA samples show varying relative intensities of 31P lines from phosphate ligands and 1H lines, especially lines from protons of coordinated water molecules. This result suggests that the number of equatorial phosphate ligands in HA could be different depending on the water content of the sample and the VO2+ concentration; complexes of different structure probably contribute to the spectra of VO2+-HA. Similar behavior can be also expected in vivo during VO2+ accumulation in bones.

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Section: Discussionsupporting

confidence: 84%

VO²⁺–hydroxyapatite complexes as models for vanadyl coordination to phosphate in bone

2013

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“…The axial phosphate interaction proposed from our results is of particular interest, as all other previous work with vanadyl has detected only equatorial phosphate coordination, corresponding to the β-and γ-phosphates of ATP. The proposed structure is consistent, however, with several crystal structures of other metal complexes with triphosphate (two containing Co(III) 49,50 and one Cd(II) 51 ) or ATP [52][53][54] as tridentate ligands. Evidence also exists for the formation of a tridentate triphosphate Rh(III) complex from NMR spectroscopy and HPLC.…”

Section: Discussionsupporting

confidence: 83%

Two-Dimensional (2D) Pulsed Electron Paramagnetic Resonance Study of VO²⁺−Triphosphate Interactions: Evidence for Tridentate Triphosphate Coordination, and Relevance To Bone Uptake and Insulin Enhancement by Vanadium Pharmaceuticals

2002

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Two- and four-pulse electron spin echo envelope modulation (ESEEM) and four-pulse two-dimensional hyperfine sublevel correlation (HYSCORE) spectroscopies have been used to determine the solution structure of a 3:1 triphosphate:vanadyl solution at pH 5.0. Limited quantitative data were extracted from the two pulse spectra; however, HYSCORE proved to be more useful in the detection and interpretation of the (31)P and (1)H couplings. Three sets of cross-peaks were observed for each nucleus. For the (31)P couplings, three sets of cross-peaks were observed in the HYSCORE spectrum, and contour line shape analysis yielded coupling constants of approximately 15, 9, and 1 MHz. HYSCORE cross-peaks in the proton region were partially overlapping; however, interpretation of the proton coupling was simplified through the use of one-dimensional four-pulse ESEEM and subsequent analysis of the sum combination peaks. Comparison of the derived isotropic and anisotropic coupling constants with results from earlier ESEEM and electron nuclear double resonance (ENDOR) studies was consistent with the presence of at least one, and most likely two, water molecules coordinated in the equatorial plane of the vanadyl cation. The vanadyl-triphosphate system was shown to be an accurate model of the in vivo vanadyl-phosphate coupling constants determined in an earlier study (Dikanov, S. A.; Liboiron, B. D.; Thompson, K. H.; Vera, E.; Yuen, V. G.; McNeill, J. H.; Orvig, C. J. Am. Chem. Soc. 1999, 121, 11004.) Comparison of these values to those found in previous spectroscopic studies of vanadyl-triphosphate interactions, along with a detailed structural interpretation, are presented. This work represents the first detection of tridentate polyphosphate coordination to the vanadyl ion, and the first observation of an axial phosphate interaction not previously reported in earlier ENDOR and pulsed electron paramagnetic resonance studies.

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“…The folding of the P 1--O4--P2--O7--P3 chain is forced by the strong hydrogen bond 02-..H2P.--O 10 which keeps the two extremities of the anion together, giving an eightmembered highly puckered ring. This hydrogen-bonded cyclization occurs in all the five compounds containing the H2P3Old-anion retrieved by an ICSD search (Inorganic Crystal Structure Database, release January 1994) (Merritt & Sundaralingam, 1981;Lutsko & Johansson, 1984;Lutsko, Lyakhov, Tuchkovskii & Palkina, 1991;Lyakhov, Palkina, Lutsko, Maximova & Chibiskova, 1990;Lyakhov, Lutsko, Tuchkovskii & Palkina, 1991). For a sixth compound containing the anion, the hydrogen coordinates are not provided (Palkina, Maksimova & Kuznetsov, 1979).…”

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confidence: 99%

Conformation and Packing of Cobalt(III) Sepulchrate Dihydrogentriphosphate Hexahydrate

Bacchi¹,

Ferranti²,

Pelizzi³

1996

Acta Crystallogr C

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Structure and chelation geometry of α,β,γ-tridentate triammine(dihydrogentriphosphato)cobalt(III), [Co(NH3)3(H2P3O10)]

Abstract: Abstract

Cited by 12 publications

References 5 publications

VO²⁺–hydroxyapatite complexes as models for vanadyl coordination to phosphate in bone

VO²⁺–hydroxyapatite complexes as models for vanadyl coordination to phosphate in bone

Two-Dimensional (2D) Pulsed Electron Paramagnetic Resonance Study of VO²⁺−Triphosphate Interactions: Evidence for Tridentate Triphosphate Coordination, and Relevance To Bone Uptake and Insulin Enhancement by Vanadium Pharmaceuticals

Conformation and Packing of Cobalt(III) Sepulchrate Dihydrogentriphosphate Hexahydrate

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Structure and chelation geometry of α,β,γ-tridentate triammine(dihydrogentriphosphato)cobalt(III), [Co(NH3)3(H2P3O10)]

Abstract: Abstract

Cited by 12 publications

References 5 publications

VO2+–hydroxyapatite complexes as models for vanadyl coordination to phosphate in bone

VO2+–hydroxyapatite complexes as models for vanadyl coordination to phosphate in bone

Two-Dimensional (2D) Pulsed Electron Paramagnetic Resonance Study of VO2+−Triphosphate Interactions: Evidence for Tridentate Triphosphate Coordination, and Relevance To Bone Uptake and Insulin Enhancement by Vanadium Pharmaceuticals

Conformation and Packing of Cobalt(III) Sepulchrate Dihydrogentriphosphate Hexahydrate

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VO²⁺–hydroxyapatite complexes as models for vanadyl coordination to phosphate in bone

VO²⁺–hydroxyapatite complexes as models for vanadyl coordination to phosphate in bone

Two-Dimensional (2D) Pulsed Electron Paramagnetic Resonance Study of VO²⁺−Triphosphate Interactions: Evidence for Tridentate Triphosphate Coordination, and Relevance To Bone Uptake and Insulin Enhancement by Vanadium Pharmaceuticals