Three-Coordinate Nickel(II) and Nickel(I) Thiolate Complexes Based on theβ-Diketiminate Ligand System
By Horn, Bettina; Limberg, Christian; Herwig, Christian & Braun, Beatrice
Published in Inorganic Chemistry
2014
Abstract
Mononuclear nickel(II) thiolate complexes [LtBuNi(SEt)] (1) and [LtBuNi(aet)] (2, aet = -S(CH2)2NH2) (LtBu = [HC(C(tBu)NC6H3(iPr)2)2]-), supported by a bulky nacnac ligand, were synthesized by treatment of the nickel(II) bromide precursor [LtBuNi(Br)] (I) with the potassium salts of ethanethiol and cysteamine, respectively. The nickel atom in 1 features a planar T-shaped environment, while the Ni ion within 2 shows a distorted square planar coordination geometry, as the aminoethanethiolate (aet) is coordinated as a chelating ligand. In 2 theβ-diketiminate ligand binds in a rarely observed κ2C,N coordination mode. Reduction of complex 1 or its benzenethiolate analogue [LtBuNi(SPh)] (II) by KC8 resulted in the formation of dinuclear NiI thiolates (K·OEt2)(K)[LtBuNi(SEt)]2 (3) and (K·OEt2)2[LtBuNi(SPh)]2 (4), respectively. In these compounds [LtBuNi(SR)]- units are held together by potassium cations produced in the reduction process. All compounds mentioned were structurally characterized by single-crystal X-ray crystallography.