57927-74-9Relevant academic research and scientific papers
Convenient synthesis and properties of (R4N)2[Ni(SAr)4] (Ar = C6H5, p-C6H4Cl, p-C6H4CH3, and m-C6H4Cl) and the structure of tetraethylammonium tetrakis(p-chlorobenzenethiolato)nickelate(II)
Rosenfield, Steven G.,Armstrong, William H.,Mascharak, Pradip K.
, p. 3014 - 3018 (2008/10/08)
Reaction of (Et4N)2NiCl4 and (R4N)(SAr) (Ar = C6H5, p-C6H4Cl, m-C6H4Cl, p-C6H4CH3) in acetonitrile affords (R4N)2-[Ni(SAr)4] in high yield. Syntheses of soluble nickel thiolates are not possible in protic solvents, where only insoluble polymeric materials are obtained. (Et4N)2[Ni(S-P-C6H4Cl)4] crystallizes in the monoclinic space group P21/c with a = 16.299 (3) ?, b = 15.464 (3) ?, c = 18.784 (3) ?, β = 109.17 (1)°, and Z = 4. The structure, refined to R = 3.5%, reveals a distorted tetrahedral arrangement of S atoms around Ni with the average Ni-S distance being 2.281 A. Two S-Ni-S angles are ～90° while the average of the other four is close to 120°. Three of the four Ni-S vectors are coplanar with the corresponding phenyl rings. Unfavorable steric contacts between the ortho H atoms and Ni or S atoms do not allow either an idealized square-planar or a tetrahedral arrangement of thiolates around Ni. This together with the tendency of the Ni-S bonds to be coplanar with the phenyl rings gives rise to the observed distortion. The NMR spectra of (R4N)2[Ni(SAr)4] are assigned and discussed.
