A study of high-valent manganese in aqueous H3PO4: Disproportionation of [MnIIIMnIV(μ-O)2(bpy)4] 3+

Joseph E. Sarneski, Linda J. Brzezinski, Brandon Anderson, Mary Didiuk, Rajesh Marchanda, Robert H. Crabtree, Gary W Brudvig, Gayle K. Schulte

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Abstract

The mixed-valence dimer [MnIIIMnIV(μ-O)2(bpy))4] 3+ (1; bpy = 2,2′-dipyridyl) has been shown to disproportionate in aqueous H3PO4. One product, [MnIV 2(μ-O)22-HPO 4)(bpy)2(H2PO4)2] (2), was isolated and characterized earlier (Inorg. Chem. 1991, 30, 2833). Here a manganese(III) product has been characterized crystallographically as [MnIII(bpy)(HPO4)(H2PO4)] x (3). 3 is a polymeric material which crystallizes in the space group P1 (No. 2) with a = 8.069(1) Å, b = 8.672(2) Å, c = 10.751(1) Å, α = 109.91(2)°, β = 102.04(1)°, and γ = 90.20(9)°. A total of 1569 unique data with I ≥ 3(σ)I were refined to values of R and Rw of 3.9 and 4.3%, respectively. The Mn(III) ions, bridged by two μ2-phosphate ligands, are 4.93 Å apart; each Mn(III) atom is bridged in this manner to two other [MnIII(bpy)(HPO4)(H2PO4)] formula units leading to a polymeric array. The aqueous chemistry of 2 and 3 has been characterized by UV-vis and EPR spectroscopy. The electrochemistry of the (IV,IV) dimer 2 in phosphate buffer shows that the complex decomposes on reduction to give the mixed-valence bis(μ-oxo) manganese dimer 1. Support for the electrochemical formation of 1 from 2 in phosphate buffer was obtained from the zero current potential curve. The Mn(III)- bpy phosphate (3) is found to disproportionate spontaneously to 1 and Mn(II) upon dissolution in phosphate buffer; for solutions of 2 or 3 in 0.1 M H3PO4 electrochemistry typical of 1 is observed. The temperature-dependent magnetic susceptibility shows strong antiferromagnetic coupling for the (IV,IV) dimer 2 with J = 79 cm-1 (ℋ = JS1·S2). The Mn(III) complex 3 shows weak antiferromagnetic coupling, consistent with the long Mn-Mn distance of 4.93 Å.

Original languageEnglish
Pages (from-to)3265-3269
Number of pages5
JournalInorganic Chemistry
Volume32
Issue number15
Publication statusPublished - 1993

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Manganese
manganese
phosphates
Dimers
Phosphates
dimers
Buffers
buffers
Electrochemistry
electrochemistry
valence
products
Magnetic susceptibility
Paramagnetic resonance
dissolving
Dissolution
Spectroscopy
Ions
chemistry
Ligands

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Sarneski, J. E., Brzezinski, L. J., Anderson, B., Didiuk, M., Marchanda, R., Crabtree, R. H., ... Schulte, G. K. (1993). A study of high-valent manganese in aqueous H3PO4: Disproportionation of [MnIIIMnIV(μ-O)2(bpy)4] 3+. Inorganic Chemistry, 32(15), 3265-3269.

A study of high-valent manganese in aqueous H3PO4 : Disproportionation of [MnIIIMnIV(μ-O)2(bpy)4] 3+. / Sarneski, Joseph E.; Brzezinski, Linda J.; Anderson, Brandon; Didiuk, Mary; Marchanda, Rajesh; Crabtree, Robert H.; Brudvig, Gary W; Schulte, Gayle K.

In: Inorganic Chemistry, Vol. 32, No. 15, 1993, p. 3265-3269.

Research output: Contribution to journalArticle

Sarneski, JE, Brzezinski, LJ, Anderson, B, Didiuk, M, Marchanda, R, Crabtree, RH, Brudvig, GW & Schulte, GK 1993, 'A study of high-valent manganese in aqueous H3PO4: Disproportionation of [MnIIIMnIV(μ-O)2(bpy)4] 3+', Inorganic Chemistry, vol. 32, no. 15, pp. 3265-3269.
Sarneski JE, Brzezinski LJ, Anderson B, Didiuk M, Marchanda R, Crabtree RH et al. A study of high-valent manganese in aqueous H3PO4: Disproportionation of [MnIIIMnIV(μ-O)2(bpy)4] 3+. Inorganic Chemistry. 1993;32(15):3265-3269.
Sarneski, Joseph E. ; Brzezinski, Linda J. ; Anderson, Brandon ; Didiuk, Mary ; Marchanda, Rajesh ; Crabtree, Robert H. ; Brudvig, Gary W ; Schulte, Gayle K. / A study of high-valent manganese in aqueous H3PO4 : Disproportionation of [MnIIIMnIV(μ-O)2(bpy)4] 3+. In: Inorganic Chemistry. 1993 ; Vol. 32, No. 15. pp. 3265-3269.
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title = "A study of high-valent manganese in aqueous H3PO4: Disproportionation of [MnIIIMnIV(μ-O)2(bpy)4] 3+",
abstract = "The mixed-valence dimer [MnIIIMnIV(μ-O)2(bpy))4] 3+ (1; bpy = 2,2′-dipyridyl) has been shown to disproportionate in aqueous H3PO4. One product, [MnIV 2(μ-O)2(μ2-HPO 4)(bpy)2(H2PO4)2] (2), was isolated and characterized earlier (Inorg. Chem. 1991, 30, 2833). Here a manganese(III) product has been characterized crystallographically as [MnIII(bpy)(HPO4)(H2PO4)] x (3). 3 is a polymeric material which crystallizes in the space group P1 (No. 2) with a = 8.069(1) {\AA}, b = 8.672(2) {\AA}, c = 10.751(1) {\AA}, α = 109.91(2)°, β = 102.04(1)°, and γ = 90.20(9)°. A total of 1569 unique data with I ≥ 3(σ)I were refined to values of R and Rw of 3.9 and 4.3{\%}, respectively. The Mn(III) ions, bridged by two μ2-phosphate ligands, are 4.93 {\AA} apart; each Mn(III) atom is bridged in this manner to two other [MnIII(bpy)(HPO4)(H2PO4)] formula units leading to a polymeric array. The aqueous chemistry of 2 and 3 has been characterized by UV-vis and EPR spectroscopy. The electrochemistry of the (IV,IV) dimer 2 in phosphate buffer shows that the complex decomposes on reduction to give the mixed-valence bis(μ-oxo) manganese dimer 1. Support for the electrochemical formation of 1 from 2 in phosphate buffer was obtained from the zero current potential curve. The Mn(III)- bpy phosphate (3) is found to disproportionate spontaneously to 1 and Mn(II) upon dissolution in phosphate buffer; for solutions of 2 or 3 in 0.1 M H3PO4 electrochemistry typical of 1 is observed. The temperature-dependent magnetic susceptibility shows strong antiferromagnetic coupling for the (IV,IV) dimer 2 with J = 79 cm-1 (ℋ = JS1·S2). The Mn(III) complex 3 shows weak antiferromagnetic coupling, consistent with the long Mn-Mn distance of 4.93 {\AA}.",
author = "Sarneski, {Joseph E.} and Brzezinski, {Linda J.} and Brandon Anderson and Mary Didiuk and Rajesh Marchanda and Crabtree, {Robert H.} and Brudvig, {Gary W} and Schulte, {Gayle K.}",
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T1 - A study of high-valent manganese in aqueous H3PO4

T2 - Disproportionation of [MnIIIMnIV(μ-O)2(bpy)4] 3+

AU - Sarneski, Joseph E.

AU - Brzezinski, Linda J.

AU - Anderson, Brandon

AU - Didiuk, Mary

AU - Marchanda, Rajesh

AU - Crabtree, Robert H.

AU - Brudvig, Gary W

AU - Schulte, Gayle K.

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N2 - The mixed-valence dimer [MnIIIMnIV(μ-O)2(bpy))4] 3+ (1; bpy = 2,2′-dipyridyl) has been shown to disproportionate in aqueous H3PO4. One product, [MnIV 2(μ-O)2(μ2-HPO 4)(bpy)2(H2PO4)2] (2), was isolated and characterized earlier (Inorg. Chem. 1991, 30, 2833). Here a manganese(III) product has been characterized crystallographically as [MnIII(bpy)(HPO4)(H2PO4)] x (3). 3 is a polymeric material which crystallizes in the space group P1 (No. 2) with a = 8.069(1) Å, b = 8.672(2) Å, c = 10.751(1) Å, α = 109.91(2)°, β = 102.04(1)°, and γ = 90.20(9)°. A total of 1569 unique data with I ≥ 3(σ)I were refined to values of R and Rw of 3.9 and 4.3%, respectively. The Mn(III) ions, bridged by two μ2-phosphate ligands, are 4.93 Å apart; each Mn(III) atom is bridged in this manner to two other [MnIII(bpy)(HPO4)(H2PO4)] formula units leading to a polymeric array. The aqueous chemistry of 2 and 3 has been characterized by UV-vis and EPR spectroscopy. The electrochemistry of the (IV,IV) dimer 2 in phosphate buffer shows that the complex decomposes on reduction to give the mixed-valence bis(μ-oxo) manganese dimer 1. Support for the electrochemical formation of 1 from 2 in phosphate buffer was obtained from the zero current potential curve. The Mn(III)- bpy phosphate (3) is found to disproportionate spontaneously to 1 and Mn(II) upon dissolution in phosphate buffer; for solutions of 2 or 3 in 0.1 M H3PO4 electrochemistry typical of 1 is observed. The temperature-dependent magnetic susceptibility shows strong antiferromagnetic coupling for the (IV,IV) dimer 2 with J = 79 cm-1 (ℋ = JS1·S2). The Mn(III) complex 3 shows weak antiferromagnetic coupling, consistent with the long Mn-Mn distance of 4.93 Å.

AB - The mixed-valence dimer [MnIIIMnIV(μ-O)2(bpy))4] 3+ (1; bpy = 2,2′-dipyridyl) has been shown to disproportionate in aqueous H3PO4. One product, [MnIV 2(μ-O)2(μ2-HPO 4)(bpy)2(H2PO4)2] (2), was isolated and characterized earlier (Inorg. Chem. 1991, 30, 2833). Here a manganese(III) product has been characterized crystallographically as [MnIII(bpy)(HPO4)(H2PO4)] x (3). 3 is a polymeric material which crystallizes in the space group P1 (No. 2) with a = 8.069(1) Å, b = 8.672(2) Å, c = 10.751(1) Å, α = 109.91(2)°, β = 102.04(1)°, and γ = 90.20(9)°. A total of 1569 unique data with I ≥ 3(σ)I were refined to values of R and Rw of 3.9 and 4.3%, respectively. The Mn(III) ions, bridged by two μ2-phosphate ligands, are 4.93 Å apart; each Mn(III) atom is bridged in this manner to two other [MnIII(bpy)(HPO4)(H2PO4)] formula units leading to a polymeric array. The aqueous chemistry of 2 and 3 has been characterized by UV-vis and EPR spectroscopy. The electrochemistry of the (IV,IV) dimer 2 in phosphate buffer shows that the complex decomposes on reduction to give the mixed-valence bis(μ-oxo) manganese dimer 1. Support for the electrochemical formation of 1 from 2 in phosphate buffer was obtained from the zero current potential curve. The Mn(III)- bpy phosphate (3) is found to disproportionate spontaneously to 1 and Mn(II) upon dissolution in phosphate buffer; for solutions of 2 or 3 in 0.1 M H3PO4 electrochemistry typical of 1 is observed. The temperature-dependent magnetic susceptibility shows strong antiferromagnetic coupling for the (IV,IV) dimer 2 with J = 79 cm-1 (ℋ = JS1·S2). The Mn(III) complex 3 shows weak antiferromagnetic coupling, consistent with the long Mn-Mn distance of 4.93 Å.

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