title: Three-coordinate nickel(II) and nickel(I) thiolate complexes based on the β-diketiminate ligand system.
abstract: Mononuclear nickel(II) thiolate complexes [L(tBu)Ni(SEt)] (1) and [L(tBu)Ni(aet)] (2, aet = (-)S(CH2)2NH2) (L(tBu) = [HC(C((t)Bu)NC6H3((i)Pr)2)2](-)), supported by a bulky nacnac ligand, were synthesized by treatment of the nickel(II) bromide precursor [L(tBu)Ni(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 the β-diketiminate ligand binds in a rarely observed κ(2)C,N coordination mode. Reduction of complex 1 or its benzenethiolate analogue [L(tBu)Ni(SPh)] (II) by KC8 resulted in the formation of dinuclear Ni(I) thiolates (K·OEt2)(K)[L(tBu)Ni(SEt)]2 (3) and (K·OEt2)2[L(tBu)Ni(SPh)]2 (4), respectively. In these compounds [L(tBu)Ni(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.
authors.affiliation: Humboldt-Universität zu Berlin , Institut für Chemie, Brook-Taylor-Str. 2, 12489 Berlin, Germany.
authors.forename: Bettina
authors.initials: B
authors.lastname: Horn
authors.forename: Christian
authors.initials: C
authors.lastname: Limberg
authors.forename: Christian
authors.initials: C
authors.lastname: Herwig
authors.forename: Beatrice
authors.initials: B
authors.lastname: Braun
mesh_terms: D002248:Carbon Monoxide / Q000737:chemistry; D056831:Coordination Complexes / Q000737:chemistry*; D007097:Imines / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D009532:Nickel / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D007097:Imines; D008024:Ligands; D013438:Sulfhydryl Compounds; D009532:Nickel; D002248:Carbon Monoxide; D010100:Oxygen