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 -/
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-31-109-ENG-38; FG05-86ER45259
- OSTI ID:
- 7256181
- Journal Information:
- Inorg. Chem.; (United States), Vol. 26:22
- Country of Publication:
- United States
- Language:
- English
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ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
GOLD COMPLEXES
CHEMICAL PREPARATION
CRYSTAL STRUCTURE
HETEROCYCLIC COMPOUNDS
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NICKEL COMPLEXES
ORGANIC SULFUR COMPOUNDS
EXPERIMENTAL DATA
COMPLEXES
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INFORMATION
MAGNETIC PROPERTIES
NUMERICAL DATA
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TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties