title: cis-Dithiolatonickel as metalloligand to dinitrosyl iron units: the di-metallic structure of Ni(μ-SR)[Fe(NO)2] and an unexpected, abbreviated metalloadamantyl cluster, Ni2(μ-SR)4[Fe(NO)2]3.
abstract: The reaction of Fe(CO)(2)(NO)(2) and Ni(N(2)S(2)) (N(2)S(2) = N,N'-Bis(2-mercaptoethyl)-1,4-diazacycloheptane) by a single CO replacement yields [Ni(N(2)S(2))]Fe(NO)(2)(CO), while an excess of Fe(CO)(2)(NO)(2) leads to triply bridging thiolate sulphurs in a cluster of core composition Ni(2)S(4)Fe(3), lacking one Fe(NO)(2) unit to complete the adamantane-like structure. This structural type was earlier identified in a Cu(I)Cl aggregate of M(II)(N(2)S(2)) (M(II) = Ni, Cu), in which complete M(II)(2)S(4)Cu(I)(4) core structures were obtained as the major, and, in the case of Cu(II)(N(2)S(2)), the incomplete Cu(II)(2)S(4)Cu(I)(3) as a minor, product. The full Ni(2)S(4)Fe(4) cluster has not yet been realized for Fe = Fe(NO)(2). Computational analysis of the NiFe-heterobimetallic complex addresses structural issues including a ∠Ni-S-Fe of 90° in the bimetallic complex.
authors.affiliation: Texas A&M University, 3255 TAMU, College Station, TX, USA.
authors.forename: Chung-Hung
authors.initials: CH
authors.lastname: Hsieh
authors.forename: Rachel B
authors.initials: RB
authors.lastname: Chupik
authors.forename: Scott M
authors.initials: SM
authors.lastname: Brothers
authors.forename: Michael B
authors.initials: MB
authors.lastname: Hall
authors.forename: Marcetta Y
authors.initials: MY
authors.lastname: Darensbourg
mesh_terms: D007501:Iron / Q000737:chemistry*; D007783:Lactones / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D009532:Nickel / Q000737:chemistry*; D009589:Nitrogen Oxides / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D011789:Quantum Theory; D013237:Stereoisomerism
chemical_list: D007783:Lactones; D008024:Ligands; D009589:Nitrogen Oxides; D009942:Organometallic Compounds; C073661:dinitrosyl iron complex; D009532:Nickel; D007501:Iron