The chemistry of [M3(CO)10(μ-dppm)](M=Ru, Os): Activating and maintaining the trinuclear core

Thermolysis of Ru3(CO)10(dppb): Activation of C H and P Ph bonds in PPh2P(CH2)4PPh2 (dppb = 1,4-bis(diphenylphosphino)butane)

“…Upon cooling to 231.2 K, the peak resolved as pseudo doublet of doublet, showing that the fluxionality is arrested. The signal broadens as the temperature is increased from 283.2 K to 303.2 K and disappears as the hydride enhancement was depleted at 323.2 K. Comparatively, the broaden hydride ligand in (l-H) 4 Ru 4 (CO) 10 (l-{Ph 2 P(CH 2 ) n PPh 2 }) (n = 1, 3, 4) is observed as temperature decreases from 300 K to 223 K [28]. The 31 P{H} NMR spectrum of 5 shows two singlet resonance belonging to two different phosphorus atom P(1) and P(2) in the diphosphine ligand.…”

“…For example, by acting as a monodentate ligand with one freely dangling phosphorus atom, chelating a single ruthenium atom within the cluster, bridging a cluster through bonding to two ruthenium atoms and linking two preformed metal clusters together [1][2][3]. The coordination of diphosphine ligands to metal cluster complexes has been proven to increase the stability of the metal atom framework of the cluster [4]. However, these complexes readily undergo pyrolysis/thermolysis reactions and result in CAH and PAC bonds cleavage and MAH and MAC bonds forming reactions [5][6][7][8].…”

Thermolysis of Ru3(CO)10(μ-dppm) and Ru3(CO)9(PRPh2)(μ-dppm) (R = Ph, H) in presence of O2: Synthesis and structure of triruthenium clusters containing a capping-oxo ligand

“…The possibility of side reactions when the incorporated phosphine (e.g., diphenylphosphine) is vulnerable to thermal transformation on cluster surface at moderate temperatures have also been examined. 10 (µ-dppm) and Ru 3 (CO) 9 (1) and Ru 3 (CO) 6 (2) High temperature reaction between Ru 3 (CO) 10 (µ-dppm) and O 2 in boiling xylene led to the formation of oxo-capped cluster Ru 3 (CO) 7 (µ 3 -CO)(µ 3 -O)(µ-dppm) (1) in 13% yield (Scheme 1). In contrast, Ru 3 (CO) 9 (PPh 3 )(µ-dppm) afforded the oxo-capped cluster Ru 3 (CO) 6 (PPh 3 )(µ 3 -CO)(µ 3 -O)(µ-dppm) (2) in 18% yield from a similar reaction with O 2 in boiling benzene (Scheme 1).…”

“…It has been known for some years that zero-valent triruthenium clusters react with elemental sulfur and its heavier congeners to afford chalcogenide-capped clusters [1][2][3][4]. In 1979, Johnson and co-workers synthesized Ru 3 (CO) 9 (µ 3 -X) 2 and Ru 3 (CO) 9 (µ-H) 2 (µ 3 -X) from the reaction of Ru 3 (CO) 12 with X n (X = S, Se, Te) in presence of CO [3].…”

Synthesis, Spectral and Electrochemical Properties and DFT Studies of Two Complexes of Ruthenium with Bis-2,3-(2-Pyridyl)Pyrazine and 4-Picoline

“…To interact with this ligand (L, I), [Ru(dmso) 4 Cl 2 ] has been chosen because of its demonstrated ability to accommodate heterocyclic neutral ligands via displacement of the coordinated moities [19][20][21] . It may be worth mentioning here that ruthenium chemistry is also important [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41] largely due to their interesting redox 35 , catalytic 22,24,30,38,41 , photophysical/photochemical 37 and biological properties 23,33,40 . The primary objective of the present study has been to synthesize mixed-ligand complexes of ruthenium incorporating ligand I and find out the coordination mode of ligand I in them.…”