Synthesis and Chemical Characterization of Complexes Containing Semiquinone Units Bridged by Pentaoxodimolybdate Groups: Structural and Electrochemical Studies of [(n-C4H9)4N]2[Mo4O10(C6H2O4)2] and [(n-c4h9)4n]3[mo 6O15(C6O6)2] and of an Analogous Tetraoxydibenzofuran Complex, [(n-c4h9)4n]2[mo 4O10(C12H4O5)2], Prepared from Metal-Mediated Radical Coupling of 1,2,4-Trihydroxybenzene Precursors

Shuncheng Liu; Shahid N. Shaikh; Jon Zubieta

doi:10.1021/ic00303a023

Synthesis and Chemical Characterization of Complexes Containing Semiquinone Units Bridged by Pentaoxodimolybdate Groups: Structural and Electrochemical Studies of [(n-C₄H₉)₄N]₂[Mo₄O₁₀(C₆H₂O₄)₂] and [(n-c4h9)4n]3[mo ₆O₁₅(C₆O₆)₂] and of an Analogous Tetraoxydibenzofuran Complex, [(n-c4h9)4n]2[mo ₄O₁₀(C₁₂H₄O₅)₂], Prepared from Metal-Mediated Radical Coupling of 1,2,4-Trihydroxybenzene Precursors

Shuncheng Liu, Shahid N. Shaikh, Jon Zubieta

Research output: Contribution to journal › Article › peer-review

37 Scopus citations

Abstract

Reaction of (Bu₄N)2[Mo₂07] with 2,5-dihydroxybenzoquinone in acetonitrile yields (Bu₄N)₂[Mo₄O₁₀(C₆H₂O₄)₂] (I), a tetranuclear complex with two [Mo₂0₅]²⁺units bridging two planar (C₆H₂O₄)^n-groups, stacked in a parallel staggered orientation. The most significant feature is the short interplanar distance between ligands of 2.67 A, allowing magnetic coupling of the radical anion semiquinoid-type ligands. Reactions of organic solvent soluble polyoxomolybdates with tetrahydroxybenzoquinone and 1,2,4-trihydroxybenzene yield the structurally analogous complexes (Bu₄N)₃[Mo₆O₁₅(C₆O₆)₂] (III) and (Bu₄N)₂(Mo₄O₁₀(C₁₂H₄O₅)₂] (IV). In contrast to I and IV, III is paramagnetic with an EPR spectrum consistent with electron localization in a ligand-centered orbital. The steric constraints introduced with the chlorine substituents of chloranilic acid, C₆C_l2O₄H₂, prevent parallel stacking of the ligands, and the mononuclear complex (Bu₄N)[MoO₂(C₆Cl₂O₄)(C₆Cl₂O₄H)] (II) is isolated from the reaction of chloranilic acid with (Bu₄N)₂[Mo₂O₇]. Crystal data for I: orthorhombic space group Pbca, a = 15.527 (3) A, b = 17.192 (3) A, c = 21.094 (4) A, Z = 4, D_calc= 1.54 g cm^-1²³; structure solution and refinement based on 1022 reflections (F₀> 6<r(F₀); Mo Ka radiation X = 0.71073 a in all cases), R = 0.060. Crystal data for II: triclinic PI, a = 10.383 (2) A, b = 13.197 (3) A, c = 14.191 (3) A, a = 88.11 (1)°, (3 = 87.57 (1)°, y = 78,11 (2)°, Z = 2, Di = 1.37 g cm^-3; 4239 reflections, R = 0.055. Crystal data for III: monoclinic Plja, a = 27.384 (5) A, b = 10.290 (2) A, c = 29.338 (6) A, 0 = 110.98 (1)°, Z = 4, D^ = 1.62 g cm^-3; 6125 reflections, R = 0.053. Crystal data for IV: monoclinic P2_x/n, a = 16.789 (3) A, b = 9.395 (2) A, c = 20.832 (3) A, 0 = 112.72 (1)°, Z = 2, D^c = 1.63 g cm'³; 3030 reflections, R = 0.052.

Original language	English (US)
Pages (from-to)	723-732
Number of pages	10
Journal	Inorganic Chemistry
Volume	28
Issue number	4
DOIs	https://doi.org/10.1021/ic00303a023
State	Published - Feb 1 1989
Externally published	Yes

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Physical and Theoretical Chemistry
Inorganic Chemistry

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Dive into the research topics of 'Synthesis and Chemical Characterization of Complexes Containing Semiquinone Units Bridged by Pentaoxodimolybdate Groups: Structural and Electrochemical Studies of [(n-C₄H₉)₄N]₂[Mo₄O₁₀(C₆H₂O₄)₂] and [(n-c4h9)4n]3[mo ₆O₁₅(C₆O₆)₂] and of an Analogous Tetraoxydibenzofuran Complex, [(n-c4h9)4n]2[mo ₄O₁₀(C₁₂H₄O₅)₂], Prepared from Metal-Mediated Radical Coupling of 1,2,4-Trihydroxybenzene Precursors'. Together they form a unique fingerprint.

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Liu, S., Shaikh, S. N., & Zubieta, J. (1989). Synthesis and Chemical Characterization of Complexes Containing Semiquinone Units Bridged by Pentaoxodimolybdate Groups: Structural and Electrochemical Studies of [(n-C₄H₉)₄N]₂[Mo₄O₁₀(C₆H₂O₄)₂] and [(n-c4h9)4n]3[mo ₆O₁₅(C₆O₆)₂] and of an Analogous Tetraoxydibenzofuran Complex, [(n-c4h9)4n]2[mo ₄O₁₀(C₁₂H₄O₅)₂], Prepared from Metal-Mediated Radical Coupling of 1,2,4-Trihydroxybenzene Precursors. Inorganic Chemistry, 28(4), 723-732. https://doi.org/10.1021/ic00303a023

Synthesis and Chemical Characterization of Complexes Containing Semiquinone Units Bridged by Pentaoxodimolybdate Groups: Structural and Electrochemical Studies of [(n-C₄H₉)₄N]₂[Mo₄O₁₀(C₆H₂O₄)₂] and [(n-c4h9)4n]3[mo ₆O₁₅(C₆O₆)₂] and of an Analogous Tetraoxydibenzofuran Complex, [(n-c4h9)4n]2[mo ₄O₁₀(C₁₂H₄O₅)₂], Prepared from Metal-Mediated Radical Coupling of 1,2,4-Trihydroxybenzene Precursors. / Liu, Shuncheng; Shaikh, Shahid N.; Zubieta, Jon.
In: Inorganic Chemistry, Vol. 28, No. 4, 01.02.1989, p. 723-732.

Research output: Contribution to journal › Article › peer-review

Liu, S, Shaikh, SN & Zubieta, J 1989, 'Synthesis and Chemical Characterization of Complexes Containing Semiquinone Units Bridged by Pentaoxodimolybdate Groups: Structural and Electrochemical Studies of [(n-C₄H₉)₄N]₂[Mo₄O₁₀(C₆H₂O₄)₂] and [(n-c4h9)4n]3[mo ₆O₁₅(C₆O₆)₂] and of an Analogous Tetraoxydibenzofuran Complex, [(n-c4h9)4n]2[mo ₄O₁₀(C₁₂H₄O₅)₂], Prepared from Metal-Mediated Radical Coupling of 1,2,4-Trihydroxybenzene Precursors', Inorganic Chemistry, vol. 28, no. 4, pp. 723-732. https://doi.org/10.1021/ic00303a023

Liu S, Shaikh SN, Zubieta J. Synthesis and Chemical Characterization of Complexes Containing Semiquinone Units Bridged by Pentaoxodimolybdate Groups: Structural and Electrochemical Studies of [(n-C₄H₉)₄N]₂[Mo₄O₁₀(C₆H₂O₄)₂] and [(n-c4h9)4n]3[mo ₆O₁₅(C₆O₆)₂] and of an Analogous Tetraoxydibenzofuran Complex, [(n-c4h9)4n]2[mo ₄O₁₀(C₁₂H₄O₅)₂], Prepared from Metal-Mediated Radical Coupling of 1,2,4-Trihydroxybenzene Precursors. Inorganic Chemistry. 1989 Feb 1;28(4):723-732. doi: 10.1021/ic00303a023

Liu, Shuncheng ; Shaikh, Shahid N. ; Zubieta, Jon. / Synthesis and Chemical Characterization of Complexes Containing Semiquinone Units Bridged by Pentaoxodimolybdate Groups : Structural and Electrochemical Studies of [(n-C₄H₉)₄N]₂[Mo₄O₁₀(C₆H₂O₄)₂] and [(n-c4h9)4n]3[mo ₆O₁₅(C₆O₆)₂] and of an Analogous Tetraoxydibenzofuran Complex, [(n-c4h9)4n]2[mo ₄O₁₀(C₁₂H₄O₅)₂], Prepared from Metal-Mediated Radical Coupling of 1,2,4-Trihydroxybenzene Precursors. In: Inorganic Chemistry. 1989 ; Vol. 28, No. 4. pp. 723-732.

@article{5e30a9cca005403dbddc8e64efe721f1,

title = "Synthesis and Chemical Characterization of Complexes Containing Semiquinone Units Bridged by Pentaoxodimolybdate Groups: Structural and Electrochemical Studies of [(n-C4H9)4N]2[Mo4O10(C6H2O4)2] and [(n-c4h9)4n]3[mo 6O15(C6O6)2] and of an Analogous Tetraoxydibenzofuran Complex, [(n-c4h9)4n]2[mo 4O10(C12H4O5)2], Prepared from Metal-Mediated Radical Coupling of 1,2,4-Trihydroxybenzene Precursors",

abstract = "Reaction of (Bu4N)2[Mo207] with 2,5-dihydroxybenzoquinone in acetonitrile yields (Bu4N)2[Mo4O10(C6H2O4)2] (I), a tetranuclear complex with two [Mo205]2+units bridging two planar (C6H2O4)n-groups, stacked in a parallel staggered orientation. The most significant feature is the short interplanar distance between ligands of 2.67 A, allowing magnetic coupling of the radical anion semiquinoid-type ligands. Reactions of organic solvent soluble polyoxomolybdates with tetrahydroxybenzoquinone and 1,2,4-trihydroxybenzene yield the structurally analogous complexes (Bu4N)3[Mo6O15(C6O6)2] (III) and (Bu4N)2(Mo4O10(C12H4O5)2] (IV). In contrast to I and IV, III is paramagnetic with an EPR spectrum consistent with electron localization in a ligand-centered orbital. The steric constraints introduced with the chlorine substituents of chloranilic acid, C6Cl2O4H2, prevent parallel stacking of the ligands, and the mononuclear complex (Bu4N)[MoO2(C6Cl2O4)(C6Cl2O4H)] (II) is isolated from the reaction of chloranilic acid with (Bu4N)2[Mo2O7]. Crystal data for I: orthorhombic space group Pbca, a = 15.527 (3) A, b = 17.192 (3) A, c = 21.094 (4) A, Z = 4, Dcalc= 1.54 g cm-123; structure solution and refinement based on 1022 reflections (F0> 60); Mo Ka radiation X = 0.71073 a in all cases), R = 0.060. Crystal data for II: triclinic PI, a = 10.383 (2) A, b = 13.197 (3) A, c = 14.191 (3) A, a = 88.11 (1)°, (3 = 87.57 (1)°, y = 78,11 (2)°, Z = 2, Di = 1.37 g cm-3; 4239 reflections, R = 0.055. Crystal data for III: monoclinic Plja, a = 27.384 (5) A, b = 10.290 (2) A, c = 29.338 (6) A, 0 = 110.98 (1)°, Z = 4, D^ = 1.62 g cm-3; 6125 reflections, R = 0.053. Crystal data for IV: monoclinic P2x/n, a = 16.789 (3) A, b = 9.395 (2) A, c = 20.832 (3) A, 0 = 112.72 (1)°, Z = 2, D^c = 1.63 g cm'3; 3030 reflections, R = 0.052.",

author = "Shuncheng Liu and Shaikh, {Shahid N.} and Jon Zubieta",

year = "1989",

month = feb,

day = "1",

doi = "10.1021/ic00303a023",

language = "English (US)",

volume = "28",

pages = "723--732",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "4",

}

TY - JOUR

T1 - Synthesis and Chemical Characterization of Complexes Containing Semiquinone Units Bridged by Pentaoxodimolybdate Groups

T2 - Structural and Electrochemical Studies of [(n-C4H9)4N]2[Mo4O10(C6H2O4)2] and [(n-c4h9)4n]3[mo 6O15(C6O6)2] and of an Analogous Tetraoxydibenzofuran Complex, [(n-c4h9)4n]2[mo 4O10(C12H4O5)2], Prepared from Metal-Mediated Radical Coupling of 1,2,4-Trihydroxybenzene Precursors

AU - Liu, Shuncheng

AU - Shaikh, Shahid N.

AU - Zubieta, Jon

PY - 1989/2/1

Y1 - 1989/2/1

N2 - Reaction of (Bu4N)2[Mo207] with 2,5-dihydroxybenzoquinone in acetonitrile yields (Bu4N)2[Mo4O10(C6H2O4)2] (I), a tetranuclear complex with two [Mo205]2+units bridging two planar (C6H2O4)n-groups, stacked in a parallel staggered orientation. The most significant feature is the short interplanar distance between ligands of 2.67 A, allowing magnetic coupling of the radical anion semiquinoid-type ligands. Reactions of organic solvent soluble polyoxomolybdates with tetrahydroxybenzoquinone and 1,2,4-trihydroxybenzene yield the structurally analogous complexes (Bu4N)3[Mo6O15(C6O6)2] (III) and (Bu4N)2(Mo4O10(C12H4O5)2] (IV). In contrast to I and IV, III is paramagnetic with an EPR spectrum consistent with electron localization in a ligand-centered orbital. The steric constraints introduced with the chlorine substituents of chloranilic acid, C6Cl2O4H2, prevent parallel stacking of the ligands, and the mononuclear complex (Bu4N)[MoO2(C6Cl2O4)(C6Cl2O4H)] (II) is isolated from the reaction of chloranilic acid with (Bu4N)2[Mo2O7]. Crystal data for I: orthorhombic space group Pbca, a = 15.527 (3) A, b = 17.192 (3) A, c = 21.094 (4) A, Z = 4, Dcalc= 1.54 g cm-123; structure solution and refinement based on 1022 reflections (F0> 60); Mo Ka radiation X = 0.71073 a in all cases), R = 0.060. Crystal data for II: triclinic PI, a = 10.383 (2) A, b = 13.197 (3) A, c = 14.191 (3) A, a = 88.11 (1)°, (3 = 87.57 (1)°, y = 78,11 (2)°, Z = 2, Di = 1.37 g cm-3; 4239 reflections, R = 0.055. Crystal data for III: monoclinic Plja, a = 27.384 (5) A, b = 10.290 (2) A, c = 29.338 (6) A, 0 = 110.98 (1)°, Z = 4, D^ = 1.62 g cm-3; 6125 reflections, R = 0.053. Crystal data for IV: monoclinic P2x/n, a = 16.789 (3) A, b = 9.395 (2) A, c = 20.832 (3) A, 0 = 112.72 (1)°, Z = 2, D^c = 1.63 g cm'3; 3030 reflections, R = 0.052.

AB - Reaction of (Bu4N)2[Mo207] with 2,5-dihydroxybenzoquinone in acetonitrile yields (Bu4N)2[Mo4O10(C6H2O4)2] (I), a tetranuclear complex with two [Mo205]2+units bridging two planar (C6H2O4)n-groups, stacked in a parallel staggered orientation. The most significant feature is the short interplanar distance between ligands of 2.67 A, allowing magnetic coupling of the radical anion semiquinoid-type ligands. Reactions of organic solvent soluble polyoxomolybdates with tetrahydroxybenzoquinone and 1,2,4-trihydroxybenzene yield the structurally analogous complexes (Bu4N)3[Mo6O15(C6O6)2] (III) and (Bu4N)2(Mo4O10(C12H4O5)2] (IV). In contrast to I and IV, III is paramagnetic with an EPR spectrum consistent with electron localization in a ligand-centered orbital. The steric constraints introduced with the chlorine substituents of chloranilic acid, C6Cl2O4H2, prevent parallel stacking of the ligands, and the mononuclear complex (Bu4N)[MoO2(C6Cl2O4)(C6Cl2O4H)] (II) is isolated from the reaction of chloranilic acid with (Bu4N)2[Mo2O7]. Crystal data for I: orthorhombic space group Pbca, a = 15.527 (3) A, b = 17.192 (3) A, c = 21.094 (4) A, Z = 4, Dcalc= 1.54 g cm-123; structure solution and refinement based on 1022 reflections (F0> 60); Mo Ka radiation X = 0.71073 a in all cases), R = 0.060. Crystal data for II: triclinic PI, a = 10.383 (2) A, b = 13.197 (3) A, c = 14.191 (3) A, a = 88.11 (1)°, (3 = 87.57 (1)°, y = 78,11 (2)°, Z = 2, Di = 1.37 g cm-3; 4239 reflections, R = 0.055. Crystal data for III: monoclinic Plja, a = 27.384 (5) A, b = 10.290 (2) A, c = 29.338 (6) A, 0 = 110.98 (1)°, Z = 4, D^ = 1.62 g cm-3; 6125 reflections, R = 0.053. Crystal data for IV: monoclinic P2x/n, a = 16.789 (3) A, b = 9.395 (2) A, c = 20.832 (3) A, 0 = 112.72 (1)°, Z = 2, D^c = 1.63 g cm'3; 3030 reflections, R = 0.052.

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