title: Synthesis of a "Masked" Terminal Nickel(II) Sulfide by Reductive Deprotection and its Reaction with Nitrous Oxide.
abstract: The addition of 1 equiv of KSCPh3 to [L(R)NiCl] (L(R) = {(2,6-iPr2C6H3)NC(R)}2CH; R = Me, tBu) in C6H6 results in the formation of [L(R)Ni(SCPh3)] (1: R = Me; 2: R = tBu) in good yields. Subsequent reduction of 1 and 2 with 2 equiv of KC8 in cold (-25 °C) Et2O in the presence of 2 equiv of 18-crown-6 results in the formation of "masked" terminal Ni(II) sulfides, [K(18-crown-6)][L(R)Ni(S)] (3: R = Me; 4: R = tBu), also in good yields. An X-ray crystallographic analysis of these complexes suggests that they feature partial multiple-bond character in their Ni-S linkages. Addition of N2O to a toluene solution of 4 provides [K(18-crown-6)][L(tBu)Ni(SN=NO)], which features the first example of a thiohyponitrite (κ(2)-[SN=NO](2-)) ligand.
authors.affiliation: Department of Chemistry and Biochemistry, University of California Santa Barbara, Santa Barbara, CA 93106 (USA).
authors.forename: Nathaniel J
authors.initials: NJ
authors.lastname: Hartmann
authors.affiliation: Department of Chemistry and Biochemistry, University of California Santa Barbara, Santa Barbara, CA 93106 (USA).
authors.forename: Guang
authors.initials: G
authors.lastname: Wu
authors.affiliation: Department of Chemistry and Biochemistry, University of California Santa Barbara, Santa Barbara, CA 93106 (USA). hayton@chem.ucsb.edu.
authors.forename: Trevor W
authors.initials: TW
authors.lastname: Hayton
mesh_terms: D018360:Crystallography, X-Ray; D008958:Models, Molecular; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D009609:Nitrous Oxide / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010084:Oxidation-Reduction
chemical_list: D009942:Organometallic Compounds; D009532:Nickel; C017558:nickel sulfide; D009609:Nitrous Oxide
keywords: coordination chemistry; nickel; nitrogen oxides; protecting groups; sulfides