On the versatility of the Hg(SePh) 2 species: Synthesis and structural characterization of bimetallic (PhSe)Hg(l)M (l = SCN À ; M = Co, Ni) polymeric chains Rafael Stieler, Gelson Manzoni de Oliveira ⇑ , Ernesto Schulz Lang ⇑ , Camila Nunes Cechin Laboratório de Materiais Inorgânicos – LMI, Universidade Federal de Santa Maria, UFSM, Departamento de Química, 97105-900 Santa Maria, RS, Brazil article info Article history: Available online 3 July 2012 Dedicated to Alfred Werner on the 100th Anniversary of his Nobel prize award in Chemistry in 1913. Keywords: Cluster compounds Mercury-clusters Bimetallic chalcogenide clusters abstract Hg(SePh) 2 react with Hg[Co(SCN) 4 ] and Hg[Ni(SCN) 4 ]Á2H 2 O in dimethylformamide (DMF) to give the new polymeric clusters [(DMF) 2 Co(NCS) 4 (HgSePh) 2 ] n and [(DMF) 2 Ni(NCS) 4 (HgSePh) 2 ] n . Both species attain in a polymeric, two-dimensional network, tetrahedral Hg II Se 2 (SCN) 2 and octahedral M II (DMF) 2 (NCS) 4 (M = Co, Ni) chains linked through SCN bridges. Although Hg and Co/Ni are not directly bound, the thio- cyanato bridges act as their ‘‘extensions’’, providing the adequate geometry for their linkages. A compar- ative discussion relating to previously obtained species is also presented. Ó 2012 Elsevier Ltd. All rights reserved. 1. Introduction It is well known that the chemistry of binary metal-chalcogen (ME) clusters deserves continuous interest, also because these compounds can be converted into electronically interesting ME nanoclusters, such as the bulky species [Cd 32 Se 14 (SePh) 36 (P n Pr 3 ) 4 ] [1], as well as into ternary MM 0 E supramolecular assemblies, like [(DMSO) 2 Co(NCS) 4 (HgTePh) 2 ] n [2]. Mercury selenide and telluride clusters and their conversions have been studied by Eichhöfer and co-workers, in order to extend optical investigations on IIb– VIa cluster molecules [3,4]. The compounds Hg(EPh) 2 (E = Se, Te; Ph = phenyl) are valuable sources of {ME} for the synthesis of binary and ternary clusters, attaining polymeric structures by weak intermolecular HgÁÁÁE interactions in the solid state [5–7], being solubilized only in coor- dinating solvents [8]. This class of compounds has been extensively used for the well-designed syntheses of binary, as well as ternary clusters, acting as templates to generate new products [6,9,10]. Given our interest in the metal organochalcogenide cluster chem- istry, we have investigated the reactions of Hg(EPh) 2 in different chemical environments and with diverse reagents. Thus, clusters with polycyclic 12-membered rings were formed exclusively from the reaction of [Hg(TePh) 2 ] with HgX 2 (X = Cl, Br, I) in pyridine, while clusters with just six-membered rings were obtained from the same reaction in dimethylsulfoxide (DMSO). In both cases the solvents were coordinated to the clusters [11]. The mercury– tellurium cluster [Hg 8 (l-n-C 3 H 7 Te) 12 (l 2 -Br)Br 3 ] was formed by the reaction of Hg(n-PrTe) 2 with HgBr 2 in DMSO; [12]. Hg(TePh) 2 reacts also with HgCl 2 and triphenylphosphine to give the clusters [(PhTe) 6 (Ph 3 P) 2 Hg 5 Cl 4 ] 2THF and [(PhTe) 8 Hg 6 Py 2 Cl 4 ]ÁPy [13]. The use of mercury bis(phenyltellurolate) was also improved for the synthesis of ternary clusters and polymers, by the reaction of Hg(TePh) 2 with AgCl/PPhMe 2 and AgClO 4 /PPh 3 , with attainment of the polymeric ternary cluster [(PhTe) 4 Ag 2 Hg 2 (Cl) 2 ] n and the single species [(PhTe) 16 Ag 4 Hg 6 Py 4 ]ÁH 2 O [14]. The synthesis of the polymeric cages [Hg 5 Cl 3 (PhSe) 7 ] n and [Hg 7 X 3 (PhSe) 11 ] n (X = Cl, Br) was carried out starting from the reaction of Hg(SePh) 2 with HgX 2 in the presence of bis(pyrimidin-2-thio)methane/ triphenylphosphine/4,4 0 -bipyridine [15]. We have also studied the influence of different ligands, coordinating solvents and reac- tion stochiometries on the formation of the reaction products of Hg(EPh) 2 (E = Se, Te) with HgX 2 (X = Cl, Br), achieving also the for- mation of the polymeric cluster [Hg 5 Br 3 (PhTe) 7 ] n [16]. Finally, the reaction of Cd(SePh) 2 with CdCl 2 and PCy 3 (tricyclohexylphos- phine) afforded the cadmium cluster [Cd 8 Cl 2 Se(SePh) 12 (PCy 3 ) 2 ] [17]. Newly we have described the synthesis, structural features and some optical aspects of the new cluster salts [M(DMF) 6 ] [Hg 8 SeX 4 (PhSe) 12 ] {M = Mg 2+ : X = Cl, Br, I; for M = Fe 2+ and Ni 2+ , X = Cl}, prepared through reaction of MgCl 2 , FeCl 2 and NiCl 2 with Hg(PhSe) 2 , using dppp (1,3-bis(diphenylphosphine)propane) as auxiliary ligand. Characteristic for all the anionic clusters is the attainment of bridges of the type [l-SePh] À by the anions [SePh] À [18]. These new selenium clusters are similar to the already known tellurium cluster Q[Hg 8 TeCl 4 (PhTe) 12 ] {Q = [Ni(DMF) 6 ] 2+ } (DMF 0277-5387/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.poly.2012.06.058 ⇑ Corresponding authors. Tel.: +55 55 3220 8980; fax: +55 55 3220 8031. E-mail addresses: manzonideo@smail.ufsm.br (G. Manzoni de Oliveira), eslang@smail.ufsm.br (E.S. Lang). Polyhedron 52 (2013) 1126–1129 Contents lists available at SciVerse ScienceDirect Polyhedron journal homepage: www.elsevier.com/locate/poly