Synthesis, molecular structure and electrochemical properties of the star-shaped dinuclear complexes [Ru2(η6-p-Me–C6H4-iPr)2(μ2-S-p-C6H4–C4H3S)3]+ and [Rh2(η5-C5Me5)2(μ2-S-p-C6H4–C4H3S)3]+

Soluble Two‐Dimensional Covalent Organometallic Polymers by (Arene)Ruthenium‐Sulfur Chemistry

“…Here, we report on a novel route to organometallic 2D polymers having high (nanometer‐scale) degree of covalent crosslinking. The quantitative, selective, and versatile reaction between Di‐μ‐chlorobis[(arene)chloro ruthenium(II)] and thiophenolato derivatives (Scheme ), is demonstrated to lead to sulfur‐linked 2D covalent (arene)ruthenium polymers. We find that the planarity of the polymer, which can be optimized with well‐chosen monomers, imposes weak interlayer interactions, hence promotes facile dispersion in solution.…”

“…[29] Here, we report on an ovel route to organometallic 2D polymers having high (nanometer-scale) degree of covalent crosslinking. The quantitative, selective, and versatile reaction be-tweenD i-m-chlorobis[(arene)chloror uthenium(II)] and thiophenolatod erivatives [30][31][32][33][34] (Scheme 1), is demonstrated to lead to sulfur-linked 2D covalent (arene)ruthenium polymers. We find that the planarity of the polymer,w hich can be optimized with well-chosen monomers, imposes weaki nterlayer interactions, hencep romotes facile dispersion in solution.T he solubility of the polymers is intrinsically ambivalent, due to the nonpolar, lipophylic branches and positive charges located about the crosslinks,m aking them readily dispersed in av arietyo fs olvents,f rom nonpolar to polar protic and aprotic ones.…”

“…We demonstrate deposition of the monolayered2 Dm aterial on highlyo riented pyrolytic graphite (HOPG) by spin-coating, and multilayered suspended thin films onto transmission electron microscopy (TEM) grids by drop-casting.Synthesis was performed in refluxing ethanol for 1h,w ith two kinds of Di-m-chlorobis[(arene)chloror uthenium(II)] ([h 6 -(HMB)RuCl 2 ] 2 )c omplexes, differing by the natureo ft he arene ligand, p-cymene (pcym) or hexamethylbenzene (HMB), and of the dithiophenol-oligo-p-phenylenes, biphenyl-4,4'-dithiol (BPDT)a nd p-terphenyl-4,4"-dithiol (TPDT). As the reactiono f thiophenolato derivatives with Di-m-chlorobis[(arene)chloro ruthenium(II)] is quantitative, [30][31][32][33][34] every dinuclearR uc omplex reacts with three thiol groups, yieldingabipyramidal Ru 2 S 3 framework coordinated with two arene ligands. The unreacted thiol groups are the active ends of the growingp olymer,a vailable for further reaction with other dinuclear Ru complexes.…”

Organometallic Ionic Liquids from Cationic Arene–Ruthenium Complexes

“…The two Ru ions are bridged by three methanethiolate anions, and the three sulfur atoms are disordered over six coplanar sites, which are all half occupied. The coordination geometries are comparable to those in [( p -cymene) 2 Ru 2 (μ-SC 6 H 4 Br) 3 )]Cl . These complexes have pseudo C 3 symmetry.…”

Reactions of 2-pyridinethiolate cobalt(III) complexes with pyridinethiolate or benzenethiolate ligands

“…2) with one l-S-bridging 2-PyS ligands and two l-S-bridging PhS ligand, which is found to consist of a closed trigonal bipyramid Co 2 S 3 framework. Many half-sandwich complexes with Rh 2 S 3 [21][22][23][24][25][26][27][28][29][30] or Ir 2 S 3 framework [27,[31][32][33][34][35][36][37][38] have been explored, but few cobalt compounds with such molecular structure have been reported. In complex 5, each metal center is coordinated to a Cp * ligand, and three sulfur atoms carrying a 2-pyridyl or phenyl group.…”