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Title: S K-edge XAS of CuⅡ, CuⅠ, and ZnⅡ oxidized Dithiolene complexes: Covalent contributions to structure and the Jahn-Teller effect

Journal Article · · Journal of Inorganic Biochemistry
 [1];  [2];  [3];  [2];  [4];  [3];  [2];  [3]
  1. Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Indiana Univ.-Purdue Univ. Indianapolis (IUPUI), Indianapolis, IN (United States)
  3. Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
+ Show Author Affiliations

We report reduced dithiolene ligands are bound to high valent Mo centers in the active site of the oxotransferase family of enzymes. Related model complexes have been studied with great insight by Prof. Holm and his colleagues. This study focuses on the other limit of dithiolene chemistry: an investigation of the 2-electron oxidized dithiolene bound to low-valent late transition metal (TM) ions (ZnII, CuI, and CuII). The bonding descriptions of the oxidized dithiolene [N,N-dimethyl piperazine 2,3-dithione (Me2Dt0)] complexes are probed using S K-edge X-ray absorption spectroscopy (XAS) and the results are correlated to density functional theory (DFT) calculations. These experimentally supported calculations are then extended to explain the different geometric structures of the three complexes. The ZnII(Me2Dt0)2 complex has only ligand-ligand repulsion so it is stabilized at the D2d symmetry limit. The CuI(Me2Dt0)2 complex has additional weak backbonding thus distorts somewhat from D2d toward D2h symmetry. The CuII(Me2Dt0)2 complex has a strong σ donor bond that leads to both a large Jahn-Teller stabilization to D2h and an additional covalent contribution to the geometry. The combined strong stabilization results in the square planar, D2h structure. This study quantifies the competition between the ligand-ligand repulsion and the change in electronic structures in determining the final geometric structures of the oxidized dithiolene complexes, and provides quantitative insights into the Jahn-Teller stabilization energy and its origin.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Biological and Environmental Research (BER); National Institutes of Health (NIH); National Institute of General Medical Sciences (NIGMS); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
Grant/Contract Number:
AC02-76SF00515; DK031450; GM061555; P30GM133894; AC02-05CH11231
OSTI ID:
1872114
Alternate ID(s):
OSTI ID: 1959790
Journal Information:
Journal of Inorganic Biochemistry, Vol. 230; ISSN 0162-0134
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

59 BASIC BIOLOGICAL SCIENCES
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
oxidized dithiolene
S K-edge X-ray absorption spectroscopy
XAS
density functional theory
DFT calculations
electronic structures
Jahn-Teller distortion
backbonding