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Title: [Cu(aq)]2+ is structurally plastic and the axially elongated octahedron goes missing

Abstract

High resolution (k = 18 Å–1 or k = 17 Å–1) copper K-edge EXAFS and MXAN (Minuit X-ray Absorption Near Edge) analyses have been used to investigate the structure of dissolved [Cu(aq)]2+ in 1,3-propanediol (1,3-P) or 1,5-pentanediol (1,5-P) aqueous frozen glasses. EXAFS analysis invariably found a single axially asymmetric 6-coordinate (CN6) site, with 4×Oeq = 1.97 Å, Oax1 = 2.22 Å, and Oax2 = 2.34 Å, plus a second-shell of 4×Owater = 3.6 Å. However, MXAN analysis revealed that [Cu(aq)]2+ occupies both square pyramidal (CN5) and axially asymmetric CN6 structures. The square pyramid included 4×H2O = 1.95 Å and 1×H2O = 2.23 Å. The CN6 sites included either a capped, near perfect, square pyramid with 5×H2O = 1.94 ± 0.04 Å and H2Oax = 2.22 Å (in 1,3-P) or a split axial configuration with 4×H2O = 1.94, H2Oax1 = 2.14 Å, and H2Oax2 = 2.28 Å (in 1,5-P). The CN6 sites also included an 8-H2O second-shell near 3.7 Å, which was undetectable about the strictly pyramidal sites. Equatorial angles averaging 94° ± 5° indicated significant departures from tetragonal planarity. MXAN assessment of the solution structure of [Cu(aq)]2+ in 1,5-P prior to freezing revealed the same structures as previously found inmore » aqueous 1M HClO4, which have become axially compressed in the frozen glasses. [Cu(aq)]2+ in liquid and frozen solutions is dominated by a 5-coordinate square pyramid, but with split axial CN6 appearing in the frozen glasses. Among these phases, the Cu–O axial distances vary across 1 Å, and the equatorial angles depart significantly from the square plane. Although all these structures remove the dx2–y2, dz2 degeneracy, no structure can be described as a Jahn-Teller (JT) axially elongated octahedron. The JT-octahedral description for dissolved [Cu(aq)]2+ should thus be abandoned in favor of square pyramidal [Cu(H2O)5]2+. The revised ligand environments have bearing on questions of the Cu(i)/Cu(ii) self-exchange rate and on the mechanism for ligand exchange with bulk water. In conclusion, the plasticity of dissolved Cu(ii) complex ions falsifies the foundational assumption of the rack-induced bonding theory of blue copper proteins and obviates any need for a thermodynamically implausible protein constraint.« less

Authors:
ORCiD logo [1];  [2];  [3]
  1. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. Lab. Nazionali di Frascati-INFN, Frascati (Italy)
  3. Stanford Univ., Stanford, CA (United States); Intel Corp., Hillsboro, OR (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1458530
Grant/Contract Number:  
AC02-76SF00515; P41GM103393
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 20; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Frank, Patrick, Benfatto, Maurizio, and Qayyum, Munzarin. [Cu(aq)]2+ is structurally plastic and the axially elongated octahedron goes missing. United States: N. p., 2018. Web. doi:10.1063/1.5024693.
Frank, Patrick, Benfatto, Maurizio, & Qayyum, Munzarin. [Cu(aq)]2+ is structurally plastic and the axially elongated octahedron goes missing. United States. doi:10.1063/1.5024693.
Frank, Patrick, Benfatto, Maurizio, and Qayyum, Munzarin. Wed . "[Cu(aq)]2+ is structurally plastic and the axially elongated octahedron goes missing". United States. doi:10.1063/1.5024693. https://www.osti.gov/servlets/purl/1458530.
@article{osti_1458530,
title = {[Cu(aq)]2+ is structurally plastic and the axially elongated octahedron goes missing},
author = {Frank, Patrick and Benfatto, Maurizio and Qayyum, Munzarin},
abstractNote = {High resolution (k = 18 Å–1 or k = 17 Å–1) copper K-edge EXAFS and MXAN (Minuit X-ray Absorption Near Edge) analyses have been used to investigate the structure of dissolved [Cu(aq)]2+ in 1,3-propanediol (1,3-P) or 1,5-pentanediol (1,5-P) aqueous frozen glasses. EXAFS analysis invariably found a single axially asymmetric 6-coordinate (CN6) site, with 4×Oeq = 1.97 Å, Oax1 = 2.22 Å, and Oax2 = 2.34 Å, plus a second-shell of 4×Owater = 3.6 Å. However, MXAN analysis revealed that [Cu(aq)]2+ occupies both square pyramidal (CN5) and axially asymmetric CN6 structures. The square pyramid included 4×H2O = 1.95 Å and 1×H2O = 2.23 Å. The CN6 sites included either a capped, near perfect, square pyramid with 5×H2O = 1.94 ± 0.04 Å and H2Oax = 2.22 Å (in 1,3-P) or a split axial configuration with 4×H2O = 1.94, H2Oax1 = 2.14 Å, and H2Oax2 = 2.28 Å (in 1,5-P). The CN6 sites also included an 8-H2O second-shell near 3.7 Å, which was undetectable about the strictly pyramidal sites. Equatorial angles averaging 94° ± 5° indicated significant departures from tetragonal planarity. MXAN assessment of the solution structure of [Cu(aq)]2+ in 1,5-P prior to freezing revealed the same structures as previously found in aqueous 1M HClO4, which have become axially compressed in the frozen glasses. [Cu(aq)]2+ in liquid and frozen solutions is dominated by a 5-coordinate square pyramid, but with split axial CN6 appearing in the frozen glasses. Among these phases, the Cu–O axial distances vary across 1 Å, and the equatorial angles depart significantly from the square plane. Although all these structures remove the dx2–y2, dz2 degeneracy, no structure can be described as a Jahn-Teller (JT) axially elongated octahedron. The JT-octahedral description for dissolved [Cu(aq)]2+ should thus be abandoned in favor of square pyramidal [Cu(H2O)5]2+. The revised ligand environments have bearing on questions of the Cu(i)/Cu(ii) self-exchange rate and on the mechanism for ligand exchange with bulk water. In conclusion, the plasticity of dissolved Cu(ii) complex ions falsifies the foundational assumption of the rack-induced bonding theory of blue copper proteins and obviates any need for a thermodynamically implausible protein constraint.},
doi = {10.1063/1.5024693},
journal = {Journal of Chemical Physics},
number = 20,
volume = 148,
place = {United States},
year = {2018},
month = {5}
}

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An understanding of the x-ray absorption near-edge structure of copper(II) imidazole complexes
journal, May 1990

  • Strange, R. W.; Alagna, L.; Durham, P.
  • Journal of the American Chemical Society, Vol. 112, Issue 11
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Dynamic Jahn–Teller Effects and Magnetic Anisotropies in Aqueous Solutions and Water–Ethanol Glasses of Copper(II) Solvates and Complexes with 2,2′‐Dipyridine
journal, February 1971

  • Noack, Manfred; Kokoszka, Gerald F.; Gordon, Gilbert
  • The Journal of Chemical Physics, Vol. 54, Issue 3
  • DOI: 10.1063/1.1674974

Multiple-scattering regime and higher-order correlations in x-ray-absorption spectra of liquid solutions
journal, October 1986


X-ray absorption spectroscopy: state-of-the-art analysis
journal, December 2002

  • Natoli, C. R.; Benfatto, M.; Della Longa, S.
  • Journal of Synchrotron Radiation, Vol. 10, Issue 1
  • DOI: 10.1107/s0909049502017247