Synthesis and Characterization of Bimetallic Ruthenium Complexes Bridged with Linear C₄H₄and C₆H₄O₂Ligands

Abstract

Reaction of Me3SiC⋮CC⋮CSiMe3 with RuHCl(CO)(PPh3)3 in CH2Cl2 produced RuCl(η1-C(C⋮CSiMe3)CHSiMe3)(CO)(PPh3)2, which on treatment with dppe gave RuCl(η1-C(C⋮CSiMe3)CHSiMe3)(CO)(PPh3)(dppe). Reaction of RuHCl(CO)(PPh3)3 with HC⋮CC⋮CH generated in situ from the reaction of Me3SiC⋮CC⋮CSiMe3 with n-Bu4NF/NH4F/H2O produced [RuCl(CO)(NH3)(PPh3)2]2(μ-CHCHCHCH), whereas the same reaction without the NH4F afforded [RuCl(CO)(PPh3)2]2(μ-CHCHCHCH). Complex [RuCl(CO)(NH3)(PPh3)2]2(μ-CHCHCHCH) reacted with excess PEt3 and t-BuNC to give [RuCl(CO)(PEt3)3]2(μ-CHCHCHCH) and {[Ru(t-BuNC)3(PPh3)2]2(μ-COCHCHCHCHCO)}Cl2, respectively. The structure of [RuCl(CO)(PEt3)3]2(μ-CHCHCHCH) has been confirmed by X-ray diffraction.

Reactivity of uranium(iv) bridged chalcogenido complexes UIV–E–UIV(E = S, Se) with elemental sulfur and selenium: synthesis of polychalcogenido-bridged uranium complexes

“…Thus, the bridging Se 4 2À unit is reminiscent to complexes of the 1,3-butadiene ligand. [51][52][53] Similar bond properties are known for polysulde ligands and can be attributed to charge localization at the rst and last selenium atom of the chain. 33,54,55 Only three selenium atoms of the Se 4 2À ligand are coordinated to each uranium center in a m-h 3 :h 3 fashion.…”

Electron delocalization in mixed-valence butadienediyl-bridged diruthenium complexes

“…. !-C4H4)](2) [16] were obtained according to the literature and [{Ru(-CO)CI(PPh3hh(~l-C4H4)] by a slight modification of the published procedure (i.e. by using neat diacetylene instead of Me3SiC4SiMe3/NBu4F/THF) [16] .…”

“…In 1998 Jia and co-workers established the double hydrometallation of diacetylene by [HRu(CO)CI(PPh 3 h] as a route to butadienediyl bridged diruthenium complexes. They prepared and characterized the dinuclear [{Ru(PPh 3 h(CO)Clh(J..!-C 4 H 4 )] (I) with coordinatively un saturated metal centers, its saturated bis-NH 3 add uct and the substitution product [{Ru(PEt 3 hCCO)Clh(J..!-C 4 H 4 )] (2) [16]. To the best of our knowledge, no electrochemical investigations have been reported on these systems.…”

Unsymmetrically Substituted Butenynyl‐Iron(II) Complexes

“…[10] Butenynyl complexes have been studied for a range of transition metals including iron, [11][12][13][14] ruthenium, [2,5,10,[15][16][17][18] osmium, [19] and platinum. [20] Various methods have been established for the synthesis of butenynyl complexes, including the addition of 1,4-disubstituted-1,3-diynes to metal hydride complexes, [2,15,21] and the addition of terminal acetylenes to either metal hydrides, [2,13,22,23] metal acetylides, [1,17,24] or metal alkenyl complexes. [22] Other methods of synthesis include the insertion of a coordinated acetylide into a metal-vinylidene bond.…”