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Title: Structural Diversities in Heterometallic Mn–Ca Cluster Chemistry from the Use of Salicylhydroxamic Acid: {MnIII4Ca2}, {MnII/III6Ca2}, {MnIII/IV8Ca}, and {MnIII8Ca2} Complexes with Relevance to Both High- and Low-Valent States of the Oxygen-Evolving Complex

Abstract

We report that one-pot reactions between the [Mn3O(O2CPh)6(py)x]+/o triangular precursors and either CaBr2·xH2O or CaCl2·6H2O, in the presence of salicylhydroxamic acid (shaH2), have afforded the heterometallic complexes [MnIII4Ca2(O2CPh)4(shi)4(H2O)3(Me2CO)] (1) and (pyH)[MnII2MnIII4Ca2Cl2(O2CPh)7(shi)4(py)4] (2), respectively, in good yields. Further reactions but using a more flexible synthetic scheme comprising the Mn(NO3)2·4H2O/Ca(NO3)2·4H2O and Mn(O2CPh)2·2H2O/Ca(ClO4)2·4H2O "metal blends" and shaH2, in the presence of external base NEt3, led to the new complexes (NHEt3)2[MnIII4MnIV4Ca(OEt)2(shi)10(EtOH)2] (3) and (NHEt3)4[MnIII8Ca2(CO3)4(shi)8] (4), respectively. In all reported compounds, the anion of the tetradentate (N,O,O,O)-chelating/bridging ligand salicylhydroxime (shi3-), resulting from the in situ metal-ion-assisted amide-iminol tautomerism of shaH2, was found to bridge both Mn and Ca atoms. Complexes 1-4 exhibit a variety of different structures, metal stoichiometries, and Mn oxidation-state descriptions; 1 possesses an overall octahedral metal arrangement, 2 can be described as a Mn4Ca2 octahedron bound to an additional Mn2unit, 3 consists of a Mn8 "ring" surrounding a CaII atom, and 4 adopts a rectangular cuboidal motif of eight Mn atoms accommodating two CaIIatoms. Solid-state direct-current magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions between the Mn centers, leading to S = 0 spin ground-state values for all complexes. Lastly, from a bioinorganic chemistry perspective, the reported compounds maymore » demonstrate some relevance to both high-valent scheme (3) and lower-oxidation-level species (1, 2, and 4) of the catalytic cycle of the oxygen-evolving complex.« less

Authors:
 [1];  [2];  [3]; ORCiD logo [4];  [4];  [5];  [5];  [6];  [6];  [6];  [7];  [6]; ORCiD logo [1]
  1. Brock Univ., St. Catharines, ON (Canada)
  2. Univ. of Patras (Greece)
  3. Univ. of Porto (Portugal)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  5. Institute of Nanoscience and Nanotechnology, NCSR “Demokritos”, Attikis (Greece)
  6. Univ. of Florida, Gainesville, FL (United States)
  7. Universitat de Barcelona (Spain)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1530297
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 56; Journal Issue: 17; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Alaimo, Alysha A., Koumousi, Evangelia S., Cunha-Silva, Luís, McCormick, Laura J., Teat, Simon J., Psycharis, Vassilis, Raptopoulou, Catherine P., Mukherjee, Shreya, Li, Chaoran, Gupta, Sayak Das, Escuer, Albert, Christou, George, and Stamatatos, Theocharis C. Structural Diversities in Heterometallic Mn–Ca Cluster Chemistry from the Use of Salicylhydroxamic Acid: {MnIII4Ca2}, {MnII/III6Ca2}, {MnIII/IV8Ca}, and {MnIII8Ca2} Complexes with Relevance to Both High- and Low-Valent States of the Oxygen-Evolving Complex. United States: N. p., 2017. Web. doi:10.1021/acs.inorgchem.7b01740.
Alaimo, Alysha A., Koumousi, Evangelia S., Cunha-Silva, Luís, McCormick, Laura J., Teat, Simon J., Psycharis, Vassilis, Raptopoulou, Catherine P., Mukherjee, Shreya, Li, Chaoran, Gupta, Sayak Das, Escuer, Albert, Christou, George, & Stamatatos, Theocharis C. Structural Diversities in Heterometallic Mn–Ca Cluster Chemistry from the Use of Salicylhydroxamic Acid: {MnIII4Ca2}, {MnII/III6Ca2}, {MnIII/IV8Ca}, and {MnIII8Ca2} Complexes with Relevance to Both High- and Low-Valent States of the Oxygen-Evolving Complex. United States. https://doi.org/10.1021/acs.inorgchem.7b01740
Alaimo, Alysha A., Koumousi, Evangelia S., Cunha-Silva, Luís, McCormick, Laura J., Teat, Simon J., Psycharis, Vassilis, Raptopoulou, Catherine P., Mukherjee, Shreya, Li, Chaoran, Gupta, Sayak Das, Escuer, Albert, Christou, George, and Stamatatos, Theocharis C. Thu . "Structural Diversities in Heterometallic Mn–Ca Cluster Chemistry from the Use of Salicylhydroxamic Acid: {MnIII4Ca2}, {MnII/III6Ca2}, {MnIII/IV8Ca}, and {MnIII8Ca2} Complexes with Relevance to Both High- and Low-Valent States of the Oxygen-Evolving Complex". United States. https://doi.org/10.1021/acs.inorgchem.7b01740. https://www.osti.gov/servlets/purl/1530297.
@article{osti_1530297,
title = {Structural Diversities in Heterometallic Mn–Ca Cluster Chemistry from the Use of Salicylhydroxamic Acid: {MnIII4Ca2}, {MnII/III6Ca2}, {MnIII/IV8Ca}, and {MnIII8Ca2} Complexes with Relevance to Both High- and Low-Valent States of the Oxygen-Evolving Complex},
author = {Alaimo, Alysha A. and Koumousi, Evangelia S. and Cunha-Silva, Luís and McCormick, Laura J. and Teat, Simon J. and Psycharis, Vassilis and Raptopoulou, Catherine P. and Mukherjee, Shreya and Li, Chaoran and Gupta, Sayak Das and Escuer, Albert and Christou, George and Stamatatos, Theocharis C.},
abstractNote = {We report that one-pot reactions between the [Mn3O(O2CPh)6(py)x]+/o triangular precursors and either CaBr2·xH2O or CaCl2·6H2O, in the presence of salicylhydroxamic acid (shaH2), have afforded the heterometallic complexes [MnIII4Ca2(O2CPh)4(shi)4(H2O)3(Me2CO)] (1) and (pyH)[MnII2MnIII4Ca2Cl2(O2CPh)7(shi)4(py)4] (2), respectively, in good yields. Further reactions but using a more flexible synthetic scheme comprising the Mn(NO3)2·4H2O/Ca(NO3)2·4H2O and Mn(O2CPh)2·2H2O/Ca(ClO4)2·4H2O "metal blends" and shaH2, in the presence of external base NEt3, led to the new complexes (NHEt3)2[MnIII4MnIV4Ca(OEt)2(shi)10(EtOH)2] (3) and (NHEt3)4[MnIII8Ca2(CO3)4(shi)8] (4), respectively. In all reported compounds, the anion of the tetradentate (N,O,O,O)-chelating/bridging ligand salicylhydroxime (shi3-), resulting from the in situ metal-ion-assisted amide-iminol tautomerism of shaH2, was found to bridge both Mn and Ca atoms. Complexes 1-4 exhibit a variety of different structures, metal stoichiometries, and Mn oxidation-state descriptions; 1 possesses an overall octahedral metal arrangement, 2 can be described as a Mn4Ca2 octahedron bound to an additional Mn2unit, 3 consists of a Mn8 "ring" surrounding a CaII atom, and 4 adopts a rectangular cuboidal motif of eight Mn atoms accommodating two CaIIatoms. Solid-state direct-current magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions between the Mn centers, leading to S = 0 spin ground-state values for all complexes. Lastly, from a bioinorganic chemistry perspective, the reported compounds may demonstrate some relevance to both high-valent scheme (3) and lower-oxidation-level species (1, 2, and 4) of the catalytic cycle of the oxygen-evolving complex.},
doi = {10.1021/acs.inorgchem.7b01740},
journal = {Inorganic Chemistry},
number = 17,
volume = 56,
place = {United States},
year = {Thu Aug 17 00:00:00 EDT 2017},
month = {Thu Aug 17 00:00:00 EDT 2017}
}

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Synthesis of a new acetate bridged Cu( ii ) building block generated 1D polymer and studies on structural, magnetic, antibacterial and anticancer properties
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The first amino acid bound manganese–calcium clusters: a {[MnIII3Ca] 2 } methylalanine complex, and a [MnIII6Ca] trigonal prism
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