Improved synthesis, solution and solid-state structure, and reactivity of [Ru₂(µ-SePh)₂(CO)₆]

Abstract

The reaction of [Ru3(CO),,] with diphenyl diselenide (1 : 1 R u : Se ratio) in refluxing tetrahydrofuran gives a mixture of [Ru,(p-SePh),(CO),] 1 and [{Ru(p-SePh),(CO),},] 2 from which complex 1 can be obtained in 50% yield. Its solid-state structure has been determined by a single crystal X-ray diffraction study [monoclinic, space group P2,/n, a = 17.305( 7), b = 16.798( 5), c = 15.254(3) A, p = 101.28(2)", Z = 81 which revealed an anti configuration of the phenyl selenide bridges. infrared and variable-temperature NMR studies indicate that only the anti isomer is present in solution. The

(Carbonyl)Iron-Selenolates: New Synthetic Methods and Reactions with Electrophiles. Crystal Structures of [(CO)6Fe2(μ-SeR)2]; R = Me3SiCH2 andp-O2NC6H4CH2, {(CO)6Fe2[μ-η2-Se,Se′-o-(SeCH2C6H4CH2Se)]}, and [(CO)6Fe2(μ-SeFe(CO)2cp)2]

“…[Ru 2 (CO) 6 (l-SePh) 2 ] from Ph 2 Se 2 and Ru 3 (CO) 12 ) [8]. In the case of tellurium, a reduction of the Ru±Ru bond in [Cp*RuCl 2 ] 2 on reaction with Me 3 SiTeR was observed, which led to the formation of a RTeTeR unit on the two ruthenium centers [9].…”

Synthesis, spectroscopic characterization and DFT study of dinuclear ruthenium sawhorse-type complexes derived from the reaction of trinuclear aggregates and (Z)-5-arylidenerhodanines

“…Mass spectra for the other complexes [Ru 2 (ArCH:Rhod) 2 (µ-ArCH:Rhod) 2 (CO) 4 ] 13a-e are found in figures S11-S14 of the Supporting Information. The results suggest that the compounds obtained are analogues to [Ru 2 (CO) 4 (C 4 H 9 COOH) 2 (µ-OOCC 4 H 9 ) 2 ] 6a[15] and [Ru 2 (CO) 4 (OHPy) 2 (µ-OPy) 2 ] 8a[18] which have two monodentate (Z)-5-arylidenerhodanines and two in a bridging mode forming chelate rings of five members.We carried out the geometry optimization of [Ru 2 (ArCH:Rhod) 2 (µ-ArCH:Rhod)2 (CO) 4 ] 13a-e and found that the (Z)-5-arylidenerhodanines sit in axial position of the two ruthenium ions (L 3 and L 4 ) and coordinate monodentate through oxygen of the rhodanine ring with a small dihedral angle (L 3 -Ru-Ru-L 4 =20°), meaning that they are coplanar to each other and perpendicular to the bridged (Z)-5-arylidenerhodanines (L 1 and L 2 ). The Ru-O bond distance is 2.266 Å while the Ru-S and Ru-N bond lengths are 2.465 Å and 2.199 Å, respectively, for [Ru 2 (4-NO 2 -ArCH:Rhod) 2 (µ-4-NO 2 -ArCH:Rhod) 2 (CO) 4 ] 13c shown in figure 5.…”

“…Reaction with 2-hydroxypyridine showed the presence of [Ru 4 H 4 (CO) 12 ] and [Ru 2 (CO) 4 (OHPy) 2 (µ-OPy) 2 ] [18] 8a and the reaction with 2-mercaptopyridine presented secondary product, the mononuclear [Ru(CO) 2 (SPy) 2 ]. Therefore, polymeric diruthenium complexes can be obtained not only by using carboxylic acids but also by ligands with particular acid-base properties.…”

Binuclear Complexes of Ruthenium and Osmium Containing Metal Metal Bonds

“…333 With the aim of elucidating the mechanism of this reduction process, the acetonitrile species [Ru 2 Cp 2 (ji-r| l -CH 2 )((i-CO)(CO)(MeCN)] was reacted with the silanes R 3 SiH (R = Me or Ph, R 3 = Me 2 Ph). Complexes of the type [Ru 2 Cp 2 (M-V-CH 2 )(H)(SiR 3 )(CO) 2 ] (191) were formed initially, but in the presence of excess R 3 SiH they gradually converted to [Ru 2 Cp 2 (u-r| 1 -CH 2 )(SiR 3 ) 2 (CO) 2 ] (192). These observations were interpreted in terms of methane formation resulting from the reduction of these silylated methylene-bridged complexes.…”