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Crystal structures of (Au(DDDT)/sub 2/)/sup 0/ and ((n-Bu)/sub 4/N)(Ni(DDDT)/sub 2/) and the ligandlike character of the isoelectronic radicals (Au(DDDT)/sub 2/)/sup 0/ and (Ni(DDDT)/sub 2/)/sup -/

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00269a027· OSTI ID:7256181
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Use of the dithiolene ligand 5,6-dihydro-1,4-dithiin-2,3-dithiolate (DDDT) led to the new gold complex (Au(DDDT)/sub 2/)/sup 0/. A single-crystal x-ray diffraction study shows that the crystal of (Au(DDDT)/sub 2/)/sup 0/ molecules packs in a dimerlike motif as found for the crystal of neutral bis(ethylenedithio)-tetrathiafulvalene (ET) molecules. In terms of valence electrons, (Au(DDDT)/sub 2/)/sup 0/ and (Ni(DDDT)/sub 2/)/sup -/ molecules are isoelectronic. The present molecular orbital calculations suggest that the metal ions of both molecules are best described as d/sup 8/ ions as expected for square-planar metal complexes, and so an unpaired electron in each molecule resides largely on the DDDT ligands with a small delocalization into the metal ion. The crystal of (Au(DDDT)/sub 2/)/sup 0/ molecules shows no ESR absorption, which is likely due to the dimerlike packing motif and can be regarded as a consequence of a strong spin-Peierls distortion. The synthesis, single-crystal x-ray structure, and magnetic susceptibility of ((n-Bu)/sub 4/N)(Ni(DDDT)/sub 2/) are also reported. In this salt, (Ni(DDDT)/sub 2/)/sup -/ molecules are found to form stacks, in contrast to those in (Et/sub 4/N)(Ni(DDDT)/sub 2/), which form layers. Unit cell parameters for (Au(DDDT)/sub 2/)/sup 0/ are space group P2//sub 1//n, a = 6.496 (1) A, b = 13.267 (4) A, c = 16.775 (3) A, ..beta.. = 94.87 (2)/sup 0/, V = 1440.5 (5) A/sup 3/, and Z = 4. For ((n-Bu)/sub 4/N)(Ni(DDDT)/sub 2/), the space group is P anti 1, a = 9.126 (6) A, b = 13.519 (9) A, c = 13,723 (5) A, ..cap alpha.. = 86.31 (4)/sup 0/, ..beta.. = 89.59 (4)/sup 0/, ..gamma.. = 77.58 (5)/sup 0/, V = 1650 (2) A (2) A /sup 3/, and Z = 2. 11 references, 6 figures, 6 tables.
Research Organization:
Argonne National Lab., IL (USA)
DOE Contract Number:
W-31109-ENG-38; FG05-86ER45259
OSTI ID:
7256181
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 26:22; ISSN INOCA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CHEMICAL PREPARATION
COMPLEXES
CRYSTAL STRUCTURE
DATA
EXPERIMENTAL DATA
GOLD COMPLEXES
HETEROCYCLIC COMPOUNDS
INFORMATION
MAGNETIC PROPERTIES
MAGNETIC SUSCEPTIBILITY
NICKEL COMPLEXES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PHYSICAL PROPERTIES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES