Conversion of core oxos to grater molecules by 4e-/4H+ reductive dehydration of the Mn4O26+ core in the manganese-oxo cubane complex Mn4O4(Ph2PO2)6: A partial model for photosynthetic water binding and activation

Wolfgang F. Ruettinger, G Charles Dismukes

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59 Citations (Scopus)

Abstract

Reaction of the Mn4O46+ 'cubane' core complex, Mn4O4L6 (1) (L = diphenylphosphinate, Ph2PO2-), with a hydrogen atom donor, phenothiazine (pzH), forms the dehydrated cluster Mn4O2L6 (2), which has lost two μ-oxo bridges by reduction to water (H2O). The formation of 2 was established by electrospray mass spectrometry, whereas FTIR spectroscopy confirmed the release of water molecules into solution during the reduction of 1. UV-vis and EPR spectroscopies established the stoichiometry and chemical form of the pzH product by showing the production of 4 equiv of the neutral pz radical. By contrast, the irreversible decomposition of 1 to individual Mn(II) ions occurs if the reduction is performed using electrons provided by various proton-lacking reductants, such as cobaltocene or electrochemical reduction. Thus, cubane 1 undergoes coupled four-electron/four-proton reduction with the release of two water molecules, a reaction formally analogous to the reverse sequence of the steps that occur during photosynthetic water oxidation leading to O2 evolution. 1H NMR of solutions of 2 reveal that all six of the phosphinate ligands exhibit paramagnetic broadening, due to coordination to Mn ions, and are magnetically equivalent. A symmetrical core structure is thus indicated. We hypothesize that this structure is produced by the dynamic averaging of phosphinato ligand coordination or exchange of μ-oxos between vacant μ-oxo sites. The paramagnetic 1H NMR of water molecules in solution shows that they are able to freely exchange with water molecules that are bound to the Mn ion(s) in 2, and this exchange can be inhibited by the addition of coordinating anions, such as chloride. Thus, 2 possesses open or labile coordination sites for water and anions, in contrast to solutions of 1, which reveal no evidence for water coordination. Complex 2 exhibits greater paramagnetism than that of 1, as seen by 1H NMR, and it possesses a broad (440 G wide) EPR absorption, centered at g = 2, that follows a Curie-Weiss temperature dependence (10-40 K) and is visible only at low temperatures, compared to EPR-silent 1. Its comparison to a spin-integration standard reveals that 2 contains 2 equiv of Mn(II), which is in agreement with the formal oxidation state of 2Mn(II)2Mn(III) that was derived from the titration. The EPR and NMR data for 2 are consistent with a loss of two of the intermanganese spin-exchange coupling pathways, versus 1, which results in two 'wingtip' Mn(II) S = 5/2 spins that are essentially magnetically uncoupled from the diamagnetic Mn2O2 base. Bond-enthalpy data, which show that O2 evolution via the reaction 1 → 2 + O2, is strongly favored thermodynamically but is not observed in the ground state due to an activation barrier, are included. This activation barrier is hypothesized to arise, in part, from the constraining effect of the facially bridging phosphinate ligands.

Original languageEnglish
Pages (from-to)1021-1027
Number of pages7
JournalInorganic Chemistry
Volume39
Issue number5
DOIs
Publication statusPublished - Mar 6 2000

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cubane
Manganese
Dehydration
dehydration
manganese
Chemical activation
activation
Molecules
Water
water
Paramagnetic resonance
molecules
Nuclear magnetic resonance
nuclear magnetic resonance
Ions
Ligands
ligands
Anions
Protons
Spectroscopy

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

@article{9d29ab2e0b43480887c23f51ee87e016,
title = "Conversion of core oxos to grater molecules by 4e-/4H+ reductive dehydration of the Mn4O26+ core in the manganese-oxo cubane complex Mn4O4(Ph2PO2)6: A partial model for photosynthetic water binding and activation",
abstract = "Reaction of the Mn4O46+ 'cubane' core complex, Mn4O4L6 (1) (L = diphenylphosphinate, Ph2PO2-), with a hydrogen atom donor, phenothiazine (pzH), forms the dehydrated cluster Mn4O2L6 (2), which has lost two μ-oxo bridges by reduction to water (H2O). The formation of 2 was established by electrospray mass spectrometry, whereas FTIR spectroscopy confirmed the release of water molecules into solution during the reduction of 1. UV-vis and EPR spectroscopies established the stoichiometry and chemical form of the pzH product by showing the production of 4 equiv of the neutral pz radical. By contrast, the irreversible decomposition of 1 to individual Mn(II) ions occurs if the reduction is performed using electrons provided by various proton-lacking reductants, such as cobaltocene or electrochemical reduction. Thus, cubane 1 undergoes coupled four-electron/four-proton reduction with the release of two water molecules, a reaction formally analogous to the reverse sequence of the steps that occur during photosynthetic water oxidation leading to O2 evolution. 1H NMR of solutions of 2 reveal that all six of the phosphinate ligands exhibit paramagnetic broadening, due to coordination to Mn ions, and are magnetically equivalent. A symmetrical core structure is thus indicated. We hypothesize that this structure is produced by the dynamic averaging of phosphinato ligand coordination or exchange of μ-oxos between vacant μ-oxo sites. The paramagnetic 1H NMR of water molecules in solution shows that they are able to freely exchange with water molecules that are bound to the Mn ion(s) in 2, and this exchange can be inhibited by the addition of coordinating anions, such as chloride. Thus, 2 possesses open or labile coordination sites for water and anions, in contrast to solutions of 1, which reveal no evidence for water coordination. Complex 2 exhibits greater paramagnetism than that of 1, as seen by 1H NMR, and it possesses a broad (440 G wide) EPR absorption, centered at g = 2, that follows a Curie-Weiss temperature dependence (10-40 K) and is visible only at low temperatures, compared to EPR-silent 1. Its comparison to a spin-integration standard reveals that 2 contains 2 equiv of Mn(II), which is in agreement with the formal oxidation state of 2Mn(II)2Mn(III) that was derived from the titration. The EPR and NMR data for 2 are consistent with a loss of two of the intermanganese spin-exchange coupling pathways, versus 1, which results in two 'wingtip' Mn(II) S = 5/2 spins that are essentially magnetically uncoupled from the diamagnetic Mn2O2 base. Bond-enthalpy data, which show that O2 evolution via the reaction 1 → 2 + O2, is strongly favored thermodynamically but is not observed in the ground state due to an activation barrier, are included. This activation barrier is hypothesized to arise, in part, from the constraining effect of the facially bridging phosphinate ligands.",
author = "Ruettinger, {Wolfgang F.} and Dismukes, {G Charles}",
year = "2000",
month = "3",
day = "6",
doi = "10.1021/ic9911421",
language = "English",
volume = "39",
pages = "1021--1027",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "5",

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TY - JOUR

T1 - Conversion of core oxos to grater molecules by 4e-/4H+ reductive dehydration of the Mn4O26+ core in the manganese-oxo cubane complex Mn4O4(Ph2PO2)6

T2 - A partial model for photosynthetic water binding and activation

AU - Ruettinger, Wolfgang F.

AU - Dismukes, G Charles

PY - 2000/3/6

Y1 - 2000/3/6

N2 - Reaction of the Mn4O46+ 'cubane' core complex, Mn4O4L6 (1) (L = diphenylphosphinate, Ph2PO2-), with a hydrogen atom donor, phenothiazine (pzH), forms the dehydrated cluster Mn4O2L6 (2), which has lost two μ-oxo bridges by reduction to water (H2O). The formation of 2 was established by electrospray mass spectrometry, whereas FTIR spectroscopy confirmed the release of water molecules into solution during the reduction of 1. UV-vis and EPR spectroscopies established the stoichiometry and chemical form of the pzH product by showing the production of 4 equiv of the neutral pz radical. By contrast, the irreversible decomposition of 1 to individual Mn(II) ions occurs if the reduction is performed using electrons provided by various proton-lacking reductants, such as cobaltocene or electrochemical reduction. Thus, cubane 1 undergoes coupled four-electron/four-proton reduction with the release of two water molecules, a reaction formally analogous to the reverse sequence of the steps that occur during photosynthetic water oxidation leading to O2 evolution. 1H NMR of solutions of 2 reveal that all six of the phosphinate ligands exhibit paramagnetic broadening, due to coordination to Mn ions, and are magnetically equivalent. A symmetrical core structure is thus indicated. We hypothesize that this structure is produced by the dynamic averaging of phosphinato ligand coordination or exchange of μ-oxos between vacant μ-oxo sites. The paramagnetic 1H NMR of water molecules in solution shows that they are able to freely exchange with water molecules that are bound to the Mn ion(s) in 2, and this exchange can be inhibited by the addition of coordinating anions, such as chloride. Thus, 2 possesses open or labile coordination sites for water and anions, in contrast to solutions of 1, which reveal no evidence for water coordination. Complex 2 exhibits greater paramagnetism than that of 1, as seen by 1H NMR, and it possesses a broad (440 G wide) EPR absorption, centered at g = 2, that follows a Curie-Weiss temperature dependence (10-40 K) and is visible only at low temperatures, compared to EPR-silent 1. Its comparison to a spin-integration standard reveals that 2 contains 2 equiv of Mn(II), which is in agreement with the formal oxidation state of 2Mn(II)2Mn(III) that was derived from the titration. The EPR and NMR data for 2 are consistent with a loss of two of the intermanganese spin-exchange coupling pathways, versus 1, which results in two 'wingtip' Mn(II) S = 5/2 spins that are essentially magnetically uncoupled from the diamagnetic Mn2O2 base. Bond-enthalpy data, which show that O2 evolution via the reaction 1 → 2 + O2, is strongly favored thermodynamically but is not observed in the ground state due to an activation barrier, are included. This activation barrier is hypothesized to arise, in part, from the constraining effect of the facially bridging phosphinate ligands.

AB - Reaction of the Mn4O46+ 'cubane' core complex, Mn4O4L6 (1) (L = diphenylphosphinate, Ph2PO2-), with a hydrogen atom donor, phenothiazine (pzH), forms the dehydrated cluster Mn4O2L6 (2), which has lost two μ-oxo bridges by reduction to water (H2O). The formation of 2 was established by electrospray mass spectrometry, whereas FTIR spectroscopy confirmed the release of water molecules into solution during the reduction of 1. UV-vis and EPR spectroscopies established the stoichiometry and chemical form of the pzH product by showing the production of 4 equiv of the neutral pz radical. By contrast, the irreversible decomposition of 1 to individual Mn(II) ions occurs if the reduction is performed using electrons provided by various proton-lacking reductants, such as cobaltocene or electrochemical reduction. Thus, cubane 1 undergoes coupled four-electron/four-proton reduction with the release of two water molecules, a reaction formally analogous to the reverse sequence of the steps that occur during photosynthetic water oxidation leading to O2 evolution. 1H NMR of solutions of 2 reveal that all six of the phosphinate ligands exhibit paramagnetic broadening, due to coordination to Mn ions, and are magnetically equivalent. A symmetrical core structure is thus indicated. We hypothesize that this structure is produced by the dynamic averaging of phosphinato ligand coordination or exchange of μ-oxos between vacant μ-oxo sites. The paramagnetic 1H NMR of water molecules in solution shows that they are able to freely exchange with water molecules that are bound to the Mn ion(s) in 2, and this exchange can be inhibited by the addition of coordinating anions, such as chloride. Thus, 2 possesses open or labile coordination sites for water and anions, in contrast to solutions of 1, which reveal no evidence for water coordination. Complex 2 exhibits greater paramagnetism than that of 1, as seen by 1H NMR, and it possesses a broad (440 G wide) EPR absorption, centered at g = 2, that follows a Curie-Weiss temperature dependence (10-40 K) and is visible only at low temperatures, compared to EPR-silent 1. Its comparison to a spin-integration standard reveals that 2 contains 2 equiv of Mn(II), which is in agreement with the formal oxidation state of 2Mn(II)2Mn(III) that was derived from the titration. The EPR and NMR data for 2 are consistent with a loss of two of the intermanganese spin-exchange coupling pathways, versus 1, which results in two 'wingtip' Mn(II) S = 5/2 spins that are essentially magnetically uncoupled from the diamagnetic Mn2O2 base. Bond-enthalpy data, which show that O2 evolution via the reaction 1 → 2 + O2, is strongly favored thermodynamically but is not observed in the ground state due to an activation barrier, are included. This activation barrier is hypothesized to arise, in part, from the constraining effect of the facially bridging phosphinate ligands.

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