Nickel bis(stilbenedithiolate)

Last updated
Nickel bis(stilbenedithiolate)
NIDPDS03.svg
Ni(S2C2Ph2)2.jpg
Names
Other names
bis[1,2-diphenyl-1,2-ethenedithiolato]nickel
bis(dithiobenzil)nickel(II)
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.044.853 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
  • InChI=1S/2C14H12S2.Ni/c2*15-13(11-7-3-1-4-8-11)14(16)12-9-5-2-6-10-12;/h2*1-10,15-16H;/p-4/b2*14-13-;
    Key: LJISAPFYPQSNRX-DEWSNNOYSA-J
  • C1=CC=C(C=C1)/C(=C(/[S-])\C2=CC=CC=C2)/[S-].C1=CC=C(C=C1)/C(=C(/[S-])\C2=CC=CC=C2)/[S-].[Ni]
Properties
C28H20NiS4
Molar mass 543.40 g·mol−1
Appearanceblack-green solid
Density 1.466 g/cm3
Melting point 260 °C (500 °F; 533 K)
Structure [1]
monoclinic
P21/n
a = 0.5836 nm, b = 1.097 nm, c = 1.836 nm
α = 90°, β = 91.4°, γ = 90°
Hazards
GHS labelling:
H317, H334, H350, H372
P260, P270, P272, P280
Safety data sheet (SDS) Bis(dithiobenzil)nickel(II). TCI
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Nickel bis(stilbenedithiolate) or bis(dithiobenzil)nickel is a coordination complex with the formula Ni(S2C2Ph2)2 (where Ph = phenyl). It exists as a black solid that gives green solutions in toluene due to a strong absorption at 855 nm. The complex is a prototype of a large family of bis(dithiolene) complexes or the formula Ni(S2C2R2)2 (R = H, alkyl, aryl). These complexes have attracted much attention as dyes. They are of academic interest because the dithiolenes are noninnocent ligands. [2] The lengths of the C-S and C-C bonds in the backbone, respectively 1.71 and 1.39 Å, are intermediate between double and single bonds. [3]

Limiting resonance structures of a R2C2S2M ring Resonance structures of dithiolene complex.png
Limiting resonance structures of a R2C2S2M ring

The complex was prepared originally by treating nickel sulfide with diphenylacetylene. [4] High yielding syntheses involve treating nickel salts with sulfided benzoin. The complex reacts with ligands to form monodithiolene complexes of the type Ni(S2C2Ph2)L2. [5]

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3
COCHCOCH
3
) and metal ions, usually transition metals. The bidentate ligand acetylacetonate is often abbreviated acac. Typically both oxygen atoms bind to the metal to form a six-membered chelate ring. The simplest complexes have the formula M(acac)3 and M(acac)2. Mixed-ligand complexes, e.g. VO(acac)2, are also numerous. Variations of acetylacetonate have also been developed with myriad substituents in place of methyl (RCOCHCOR′). Many such complexes are soluble in organic solvents, in contrast to the related metal halides. Because of these properties, acac complexes are sometimes used as catalyst precursors and reagents. Applications include their use as NMR "shift reagents" and as catalysts for organic synthesis, and precursors to industrial hydroformylation catalysts. C
5
H
7
O
2
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References

  1. Sartain, D.; Truter, Mary R. (1967). "The crystal structure of bis(dithiobenzil)nickel". Journal of the Chemical Society A: Inorganic, Physical, Theoretical: 1264. doi:10.1039/J19670001264.
  2. Karlin, K. D.; Stiefel, E. I., Eds. “Progress in Inorganic Chemistry, Dithiolene Chemistry: Synthesis, Properties, and Applications” Wiley-Interscience: New York, 2003. ISBN   0-471-37829-1
  3. Miao, Qingqing; Gao, Junxiong; Wang, Zeqing; Yu, Hang; Luo, Yi; Ma, Tingli (2011). "Syntheses and Characterization of Several Nickel Bis(dithiolene) Complexes with Strong and Broad Near-IR Absorption". Inorganica Chimica Acta. 376: 619–627. doi:10.1016/j.ica.2011.07.046.
  4. Schrauzer, G. N.; Mayweg, V. (1962). "Reaction of Diphenylacetylene with Nickel Sulfides". Journal of the American Chemical Society. 84 (16): 3221. doi:10.1021/ja00875a061.
  5. Obanda, Antony; Martinez, Kristina; Schmehl, Russell H.; Mague, Joel T.; Rubtsov, Igor V.; MacMillan, Samantha N.; Lancaster, Kyle M.; Sproules, Stephen; Donahue, James P. (2017). "Expanding the Scope of Ligand Substitution from [M(S2C2Ph2] (M = Ni2+, Pd2+, Pt2+) to Afford New Heteroleptic Dithiolene Complexes" (PDF). Inorganic Chemistry. 56 (17): 10257–10267. doi:10.1021/acs.inorgchem.7b00971. PMID   28820242.