Studies of the oxovanadium-organophosphonate system: Hydrothermal synthesis and crystal structure of the mixed valence cluster

José Salta; Jon Zubieta

doi:10.1007/BF02764114

Studies of the oxovanadium-organophosphonate system: Hydrothermal synthesis and crystal structure of the mixed valence cluster

José Salta, Jon Zubieta

Department of Chemistry

Research output: Contribution to journal › Review article › peer-review

6 Scopus citations

Abstract

The room temperature reaction of (Bu₄N)₃V₅O₁₄ with PhPO₃H₂ in methanol yields the pentanuclear V(V) cluster (Bu₄N)[V₅O₇(OCH₃) ₂(PhPO₃)₅]· CH₃OH (1·CH₃OH). In contrast, the hydrothermal reaction of (Ph₄P) [VO₂Cl₂], PhPO₃H₂ and (NH₄)H₂PO₄ at 125°C for 96 hr yields the mixed valence V(IV)/V(V) species (Ph₄P)₂[V₅O₉(PhPO₃) ₃(PhPO₃H)₂] (3). While the anions of both 1 and 3 exhibit a pentanuclear core, the structural consequences of 1-electron reduction of the fully oxidized cluster of 1 to produce 3 are quite dramatic, including reduction in coordination numbers at two vanadium sites and protonation of two phosphonate oxygen sites with concomitant structural reorganization. Crystal data: 1, monoclinic P2₁/n, a = 12.167(2) Å, b = 23.348(5) Å, c = 22.508(5) Å, β = 98.49(2)°, V = 6323.9(19) Å³, Z = 4, D_calc = 1.558 g cm^-3; 3, triclinic, P1, a = 13.478(3) Å, b = 14.399(3) Å, c = 23.638(5) Å, α = 72.53(2)°, β = 85.58(2)°, γ = 69.88(4)°, V = 4107.0(16) Å³, Z = 2, D_calc = 1.479 g cm^-3.

Original language	English (US)
Pages (from-to)	361-380
Number of pages	20
Journal	Journal of Cluster Science
Volume	8
Issue number	3
DOIs	https://doi.org/10.1007/BF02764114
State	Published - Sep 1997

Keywords

Metal oxide clusters
Mixed valence compounds
Oxovanadium phosphonate clusters

ASJC Scopus subject areas

Biochemistry
General Chemistry
General Materials Science
Condensed Matter Physics

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10.1007/BF02764114

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@article{bd006dcc1778487cb1ea6693be9c4935,

title = "Studies of the oxovanadium-organophosphonate system: Hydrothermal synthesis and crystal structure of the mixed valence cluster",

abstract = "The room temperature reaction of (Bu4N)3V5O14 with PhPO3H2 in methanol yields the pentanuclear V(V) cluster (Bu4N)[V5O7(OCH3) 2(PhPO3)5]· CH3OH (1·CH3OH). In contrast, the hydrothermal reaction of (Ph4P) [VO2Cl2], PhPO3H2 and (NH4)H2PO4 at 125°C for 96 hr yields the mixed valence V(IV)/V(V) species (Ph4P)2[V5O9(PhPO3) 3(PhPO3H)2] (3). While the anions of both 1 and 3 exhibit a pentanuclear core, the structural consequences of 1-electron reduction of the fully oxidized cluster of 1 to produce 3 are quite dramatic, including reduction in coordination numbers at two vanadium sites and protonation of two phosphonate oxygen sites with concomitant structural reorganization. Crystal data: 1, monoclinic P21/n, a = 12.167(2) {\AA}, b = 23.348(5) {\AA}, c = 22.508(5) {\AA}, β = 98.49(2)°, V = 6323.9(19) {\AA}3, Z = 4, Dcalc = 1.558 g cm-3; 3, triclinic, P1, a = 13.478(3) {\AA}, b = 14.399(3) {\AA}, c = 23.638(5) {\AA}, α = 72.53(2)°, β = 85.58(2)°, γ = 69.88(4)°, V = 4107.0(16) {\AA}3, Z = 2, Dcalc = 1.479 g cm-3.",

keywords = "Metal oxide clusters, Mixed valence compounds, Oxovanadium phosphonate clusters",

author = "Jos{\'e} Salta and Jon Zubieta",

year = "1997",

month = sep,

doi = "10.1007/BF02764114",

language = "English (US)",

volume = "8",

pages = "361--380",

journal = "Journal of Cluster Science",

issn = "1040-7278",

publisher = "Springer New York",

number = "3",

}

TY - JOUR

T1 - Studies of the oxovanadium-organophosphonate system

T2 - Hydrothermal synthesis and crystal structure of the mixed valence cluster

AU - Salta, José

AU - Zubieta, Jon

PY - 1997/9

Y1 - 1997/9

N2 - The room temperature reaction of (Bu4N)3V5O14 with PhPO3H2 in methanol yields the pentanuclear V(V) cluster (Bu4N)[V5O7(OCH3) 2(PhPO3)5]· CH3OH (1·CH3OH). In contrast, the hydrothermal reaction of (Ph4P) [VO2Cl2], PhPO3H2 and (NH4)H2PO4 at 125°C for 96 hr yields the mixed valence V(IV)/V(V) species (Ph4P)2[V5O9(PhPO3) 3(PhPO3H)2] (3). While the anions of both 1 and 3 exhibit a pentanuclear core, the structural consequences of 1-electron reduction of the fully oxidized cluster of 1 to produce 3 are quite dramatic, including reduction in coordination numbers at two vanadium sites and protonation of two phosphonate oxygen sites with concomitant structural reorganization. Crystal data: 1, monoclinic P21/n, a = 12.167(2) Å, b = 23.348(5) Å, c = 22.508(5) Å, β = 98.49(2)°, V = 6323.9(19) Å3, Z = 4, Dcalc = 1.558 g cm-3; 3, triclinic, P1, a = 13.478(3) Å, b = 14.399(3) Å, c = 23.638(5) Å, α = 72.53(2)°, β = 85.58(2)°, γ = 69.88(4)°, V = 4107.0(16) Å3, Z = 2, Dcalc = 1.479 g cm-3.

AB - The room temperature reaction of (Bu4N)3V5O14 with PhPO3H2 in methanol yields the pentanuclear V(V) cluster (Bu4N)[V5O7(OCH3) 2(PhPO3)5]· CH3OH (1·CH3OH). In contrast, the hydrothermal reaction of (Ph4P) [VO2Cl2], PhPO3H2 and (NH4)H2PO4 at 125°C for 96 hr yields the mixed valence V(IV)/V(V) species (Ph4P)2[V5O9(PhPO3) 3(PhPO3H)2] (3). While the anions of both 1 and 3 exhibit a pentanuclear core, the structural consequences of 1-electron reduction of the fully oxidized cluster of 1 to produce 3 are quite dramatic, including reduction in coordination numbers at two vanadium sites and protonation of two phosphonate oxygen sites with concomitant structural reorganization. Crystal data: 1, monoclinic P21/n, a = 12.167(2) Å, b = 23.348(5) Å, c = 22.508(5) Å, β = 98.49(2)°, V = 6323.9(19) Å3, Z = 4, Dcalc = 1.558 g cm-3; 3, triclinic, P1, a = 13.478(3) Å, b = 14.399(3) Å, c = 23.638(5) Å, α = 72.53(2)°, β = 85.58(2)°, γ = 69.88(4)°, V = 4107.0(16) Å3, Z = 2, Dcalc = 1.479 g cm-3.

KW - Metal oxide clusters

KW - Mixed valence compounds

KW - Oxovanadium phosphonate clusters

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U2 - 10.1007/BF02764114

DO - 10.1007/BF02764114

M3 - Review article

AN - SCOPUS:27844501558

SN - 1040-7278

VL - 8

SP - 361

EP - 380

JO - Journal of Cluster Science

JF - Journal of Cluster Science

IS - 3

ER -

Studies of the oxovanadium-organophosphonate system: Hydrothermal synthesis and crystal structure of the mixed valence cluster

Abstract

Keywords

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