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Title: Expanding the Chemistry of Rhenium Metal–Metal Bonded Fluoro Complexes: Facile Preparation and Characterization of Paddlewheel Complexes

Quadruply bonded rhenium(III) dimers with the stoichiometry Re 2L 4F 2 (1, L = hexahydro-2H-pyrimido[1,2a]pyrimidinate (hpp ); 2, L = diphenyl formamidinate (dpf )) were prepared from the solid-state melt reactions (SSMRs) between (NH 4) 2[Re 2F 8]·2H 2O and HL. Then those compounds were characterized in the solid state by single-crystal X-ray diffraction and in solution by UV–visible spectroscopy and cyclic voltammetry. The compound [Re 2(hpp) 4F 2]PF 6 (3) was prepared from the one-electron oxidation of Re 2(hpp) 4F 2 with [Cp 2Fe]PF 6. Compounds 1–3 are isostructural with the corresponding chloro derivatives. In summation, compound 1 undergoes two one-electron oxidations. Comparison with its higher halogen homologues reveals that Re 2(hpp) 4F 2 (1) is more easily oxidized than its chloro and bromo analogues.
Authors:
ORCiD logo [1] ;  [2] ;  [3] ;  [1]
  1. Univ. of Nevada, Las Vegas, NV (United States). Dept. of Chemistry and Biochemistry
  2. Univ. of Nevada, Las Vegas, NV (United States). Dept. of Chemistry and Biochemistry; Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  3. Freie Univ., Berlin (Germany). Dept. of Chemistry and Biochemistry
Publication Date:
Grant/Contract Number:
NA0003180; NA0000979
Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 1; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Research Org:
Univ. of Nevada, Las Vegas, NV (United States)
Sponsoring Org:
USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1413997

Balasekaran, Samundeeswari Mariappan, Sattelberger, Alfred P., Hagenbach, Adelheid, and Poineau, Frederic. Expanding the Chemistry of Rhenium Metal–Metal Bonded Fluoro Complexes: Facile Preparation and Characterization of Paddlewheel Complexes. United States: N. p., Web. doi:10.1021/acs.inorgchem.7b02519.
Balasekaran, Samundeeswari Mariappan, Sattelberger, Alfred P., Hagenbach, Adelheid, & Poineau, Frederic. Expanding the Chemistry of Rhenium Metal–Metal Bonded Fluoro Complexes: Facile Preparation and Characterization of Paddlewheel Complexes. United States. doi:10.1021/acs.inorgchem.7b02519.
Balasekaran, Samundeeswari Mariappan, Sattelberger, Alfred P., Hagenbach, Adelheid, and Poineau, Frederic. 2017. "Expanding the Chemistry of Rhenium Metal–Metal Bonded Fluoro Complexes: Facile Preparation and Characterization of Paddlewheel Complexes". United States. doi:10.1021/acs.inorgchem.7b02519.
@article{osti_1413997,
title = {Expanding the Chemistry of Rhenium Metal–Metal Bonded Fluoro Complexes: Facile Preparation and Characterization of Paddlewheel Complexes},
author = {Balasekaran, Samundeeswari Mariappan and Sattelberger, Alfred P. and Hagenbach, Adelheid and Poineau, Frederic},
abstractNote = {Quadruply bonded rhenium(III) dimers with the stoichiometry Re2L4F2 (1, L = hexahydro-2H-pyrimido[1,2a]pyrimidinate (hpp–); 2, L = diphenyl formamidinate (dpf–)) were prepared from the solid-state melt reactions (SSMRs) between (NH4)2[Re2F8]·2H2O and HL. Then those compounds were characterized in the solid state by single-crystal X-ray diffraction and in solution by UV–visible spectroscopy and cyclic voltammetry. The compound [Re2(hpp)4F2]PF6 (3) was prepared from the one-electron oxidation of Re2(hpp)4F2 with [Cp2Fe]PF6. Compounds 1–3 are isostructural with the corresponding chloro derivatives. In summation, compound 1 undergoes two one-electron oxidations. Comparison with its higher halogen homologues reveals that Re2(hpp)4F2 (1) is more easily oxidized than its chloro and bromo analogues.},
doi = {10.1021/acs.inorgchem.7b02519},
journal = {Inorganic Chemistry},
number = 1,
volume = 57,
place = {United States},
year = {2017},
month = {12}
}