title: Extended network thiocyanate- and tetracyanoethanide-based first-row transition metal complexes.
abstract: Linear chain thiocyanate complexes of M(NCS)(2)(OCMe(2))(2) (M = Fe, Mn, Cr) composition have been prepared and structurally, chemically, and magnetically characterized. Fe(NCS)(2)(OCMe(2))(2) exhibits metamagnetic-like behavior, and orders as an antiferromagnet at 6 K. The Mn and Cr compounds are antiferromagnets with T(c) of 30 and 50 K, respectively, with J/k(B) = -3.5 (-2.4 cm(-1)) and -9.9 K (-6.9 cm(-1)), respectively, when fit to one-dimensional (1-D) Fisher chain model (H = -2JS(i)·S(j)). Co(NCS)(2) was prepared by a new synthetic route, and powder diffraction was used to determine its structure to be a two-dimensional (2-D) layer with μ(N,S,S)-NCS motif, and it is an antiferromagnet (T(c) = 22 K; θ = -33 K for T > 25 K). M(NCS)(2)(OCMe(2))(2) (M = Fe, Mn) and Co(NCS)(2) react with (NBu(4))(TCNE) in dichloromethane to form M(TCNE)[C(4)(CN)(8)](1/2), and in acetone to form M[C(4)(CN)(8)](OCMe(2))(2) (M = Fe, Mn, Co). These materials possess μ(4)-[C(4)(CN)(8)](2-) that form 2-D layered structural motifs, which exhibit weak antiferromagnetic coupling. Co(TCNE)[C(4)(CN)(8)](1/2) behaves as a paramagnet with strong antiferromagnetic coupling (θ = -50 K).
authors.affiliation: Department of Chemistry, University of Utah, Salt Lake City, Utah 84112-0850, USA.
authors.forename: Endrit
authors.initials: E
authors.lastname: Shurdha
authors.forename: Saul H
authors.initials: SH
authors.lastname: Lapidus
authors.forename: Peter W
authors.initials: PW
authors.lastname: Stephens
authors.forename: Curtis E
authors.initials: CE
authors.lastname: Moore
authors.forename: Arnold L
authors.initials: AL
authors.lastname: Rheingold
authors.forename: Joel S
authors.initials: JS
authors.lastname: Miller
mesh_terms: D008958:Models, Molecular; D009570:Nitriles / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D013696:Temperature; D013861:Thiocyanates / Q000737:chemistry*; D028561:Transition Elements / Q000737:chemistry*
chemical_list: D009570:Nitriles; D009942:Organometallic Compounds; D013861:Thiocyanates; D028561:Transition Elements; C031760:thiocyanate