Two different types of 2-thienyl bridge in dinuclear manganese and rhenium compounds

Reaction of [Ru3(CO)12] with tri(2-furyl)phosphine: Di- and tri-substituted triruthenium and phosphido-bridged diruthenium complexes

“…It is well-documented that heterodifunctional ligands exhibit very interesting properties, such as selective binding to metal ions of different types, dynamic behavior via reversible dissociation of the weaker metal-ligand bond and stereoelectronic control of the coordination sphere of the metal [23]. Deeming and co-workers have reported that the reaction of [Ru 3 (CO) 12 ] with diphenyl(2-thienyl)phosphine gives, in addition to the phosphine derivatives of the trinuclear cluster, the carbon-hydrogen activated products [Ru 3 (CO) 9 (l 3 -Ph 2 PC 4 H 2 S)(l-H)] and [Ru 3 (CO) 8 (Ph 2 PC 4 H 3 S)(l 3 -Ph 2 PC 4 H 2 S)(l-H)], the former reacting further with [Ru 3 (CO) 12 ] to yield the thiophyne cluster [Ru 4 (CO) 11 (l 3 -Ph 2 PC 4 H 2 S)(l 4 -PPh)(l 4 -C 4 H 2 S)(l-H)] resulting from phosphorus-carbon bond cleavage [8]. The CO substitution reaction of [Ru 3 (CO) 12 ] by tertiary phosphines occurs favorably via electron-transfer catalysis conditions using sodium diphenylketyl [22,24].…”

“…More recently, the reactivity of group 8 metal carbonyls with functionalized phosphines such as diphenyl(2-thienyl)phosphine [8][9][10][11], di(2-thienyl)phenylphosphine [12], diphenyl(benzothienyl)phosphine [12], tri(2-thienyl)phosphine [13][14][15], diphenyl(2-pyridyl)phosphine [16][17][18][19][20][21] and 2-indolyl phosphine [22] have attracted considerable attention since the presence of a second coordinating atom provides a diversity of coordination modes. It is well-documented that heterodifunctional ligands exhibit very interesting properties, such as selective binding to metal ions of different types, dynamic behavior via reversible dissociation of the weaker metal-ligand bond and stereoelectronic control of the coordination sphere of the metal [23].…”

Thermal transformations of tris(2-thienyl)phosphine (PTh3) at low-valent ruthenium cluster centers: Part I. Carbon–hydrogen, carbon–phosphorus and carbon–sulfur bond activation yielding Ru3(CO)8L{μ-Th2P(C4H2S)}(μ-H) (L = CO, PTh3), Ru3(CO)7(μ-PTh2)2(μ3-η2-C4H2S), Ru4(CO)9(μ-CO)2(μ4-η2-C4H2S)(μ4-PTh) and Ru5(CO)11(μ-PTh2)(μ4-η4-C4H3)(μ4-S)

“…No species with the PTh 3 acting as a bidentate P,S donor ligand have been observed, although this particular coordination has been reported by Deeming and co-workers in some dirhenium compounds. 50 …”

Syntheses and Fluxional Processes of Diphenyl(2‐thienyl)phosphane Derivatives of Triosmium Clusters

“…diphenyl(2-thienyl)phosphane] have therefore been used to bring the heterocycle into the coordination sphere of transition-metal clusters through the phosphane moiety of the ligand. [18][19][20] Treatment of diphenyl(2-thienyl)phosphane with [Ru 3 (CO) 12 ] has led to the incorporation of the thiophene ring into tri-and tetraruthenium clusters by cyclometallation and C-P bond cleavage of the ligand. [20] Here we report the reactions of [Os 3 10 ] with diphenyl(2-thienyl)phosphane, Ph 2 P(C 4 H 3 S), which have been undertaken in an effort to achieve C-P and C-S bond cleavage of the ligand.…”