High-nuclearity clusters of ruthenium. Synthesis and crystal and molecular structure of heptadecacarbonyldi-.mu.4-sulfido(.eta.-toluene)octaruthenium

Reactions of trans-[RuCl2(CO)2(PEt3)2] with 1,1-dithiolates: Stepwise formation of cis-[Ru(CO)(PEt3)(S2X)] (X=CNMe2, CNEt2, COEt, P(OEt)2, PPh2)

“…1. The carbonyl and phosphine lie at right angles [C(1)-Ru(1)-P(1) 89.70 (11)°] at the octahedral ruthenium(II) centre, the coordination sphere of which is completed by a cis disposition of the two small bite angle [S(2)-Ru (1) (9), Ru(1)-S(4) 2.4767(9) Å ], the longer distances being those trans to the carbonyl and phosphine; a similar trans-influence being exhibited by the two.…”

“…Thus, with cis-[Ru(CO) 2 (S 2 CNEt 2 ) 2 ], pentanuclear [Ru 5 -(l 4 -S) 2 (l-CNEt 2 ) 2 (CO) 11 ] is the major product [3], while with cis-[Ru(CO) 2 (S 2 CNMe 2 ) 2 ], octanuclear [Ru 8 (l 4 -S) 3 -(l 3 -S)(l-CNMe 2 ) 2 (CO) 16 ] has been isolated and crystallographically characterized [4]. The mode of formation of these clusters is unknown, but the likely initial process is one of carbonyl loss from the bis(dithiocarbamate) complexes to afford dimeric [Ru(CO)(S 2 CNR 2 )(l-S 2 CNR 2 )] 2 (R = Me, Et), a process known to occur cleanly in the presence of trimethylamine N-oxide [5].…”

Heptacarbonylbis(triphenylphosphine)bis(μ3-tellurium)-triiron

“…This same axial-equatorial coordination scheme was also observed in (PPh3)aRu3(fO)6(/z3-Te)2 (Mathur, Thimmappa & Rheingold, 1990) which contains a third phosphine ligand on an apical Ru atom. However, previous reports of structures containing a similar metalchalcogen cluster framework indicate a preference for equatorial coordination of bulky ligands: (C3PhE)Fea(CO)8(/z3-S)2 (Dettlaf, Hubener, Klimes & Weiss, 1982), (CaH2S2)Fea(CO)8(/x3-S)2 (Benoit, Marouille & Patin, 1982) and (MeENH)-Fe3(CO)8(/z3-S)2 (Adams & Babin, 1986). Comparing the bond lengths of the phosphine ligands reveals, however, that the axial triphenylphosphine ligand has the shorter bond: the axial Fe(2)--P(2) bond is 2.214 (1),~ and the equatorial Fe(1)--P(1) bond is 2.274(1)A.…”

Facile C−S Bond Activation of Levamisole Hydrochloride on a Triruthenium Cluster Core

“…[12] The sulfide derivatives [Ru 3 (µ 3 -S)(CO) 10 ], [Ru 3 (µ 3 -S)(µ-H) 2 (CO) 9 ] and [Ru 4 (µ 4 -S)(CO) 11 ] have been prepared from [Ru 3 (CO) 12 ] and thiophenol. [13] The reaction of [Ru 3 (CO) 12 ] with 2-(diphenylphosphanyl)thiophenol gives the phenyl derivative [Ru 3 (µ 3 -S)(µ-C 6 H 5 )(µ-PPh 2 )(PPh 3 )(CO) 6 ], in which both CϪS and CϪP bonds have been activated. [14] Further studies on the synthesis of levamisole-derived metal complexes are underway.…”