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Heterotrimetallic Mixed‐Valent Molecular Precursors Containing Periodic Table Neighbors: Assignment of Metal Positions and Oxidation States

Journal Article · · Angewandte Chemie (International Edition)
 [1];  [2];  [2];  [2];  [2];  [3];  [4];  [5];  [5];  [2]
  1. Department of Chemistry University at Albany State University of New York Albany NY 12222 USA, Department of Materials Science and Engineering Cornell University Ithaca NY 14850 USA
  2. Department of Chemistry University at Albany State University of New York Albany NY 12222 USA
  3. Department of Chemistry University of Chicago Chicago IL 60637 USA
  4. NSF's ChemMatCARS Center for Advanced Radiation Source The University of Chicago Argonne IL 60439 USA
  5. Department of Chemistry Illinois Institute of Technology Chicago IL 60616 USA
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Abstract

A known trinuclear structure was used to design the heterobimetallic mixed‐valent, mixed‐ligand molecule [Co II (hfac) 3 −Na−Co III (acac) 3 ] ( 1 ). This was used as a template structure to develop heterotrimetallic molecules [Co II (hfac) 3 −Na−Fe III (acac) 3 ] ( 2 ) and [Ni II (hfac) 3 −Na−Co III (acac) 3 ] ( 3 ) via isovalent site‐specific substitution at either of the cobalt positions. Diffraction methods, synchrotron resonant diffraction, and multiple‐wavelength anomalous diffraction were applied beyond simple structural investigation to provide an unambiguous assignment of the positions and oxidation states for the periodic table neighbors in the heterometallic assemblies. Molecules of 2 and 3 are true heterotrimetallic rather than a statistical mixture of two heterobimetallic counterparts. Trinuclear platform 1 exhibits flexibility in accommodating a variety of di‐ and trivalent metals, which can be further utilized in the design of molecular precursors for the NaMM′O 4 functional oxide materials.

Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1631760
Alternate ID(s):
OSTI ID: 1637962
OSTI ID: 22973494
Journal Information:
Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 24 Vol. 59; ISSN 1433-7851
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

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