Synthesis of [Ru3(CO)9(μ-dppf){P(C4H3E)3}] (E = O, S) and thermally induced cyclometalation to form [(μ-H)Ru3(CO)7(μ-dppf){μ3-(C4H3E)2P(C4H2E)}] (dppf = 1,1′-bis(diphenylphosphino)ferrocene)

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

“…The thermolysis of Ru 3 (CO) 10 (dppb) 1 in refluxing toluene for 4 h followed by the usual chromatographic separation afforded four triruthenium compounds, Ru 3 (CO) 7 (l 3 -C 6 H 4 )(l-PPh 2 ){l-PPhBu n } 2, Ru 5 (CO) 14 (l 4 -PPh){PPh 2 Bu n } 3, Ru 3 (CO) 8 (l 3 -PPh 2 CH 2 CH 2 CCHPPh 2 (l-H) 4 and Ru 3 (CO) 8 (l 3 -P(Ph)CHCHCH 2 CH 2 PPh 2 )(l-H) 5 (Scheme 1). The new compounds have been characterized by elemental analysis, infrared spectroscopy, 1 H and 31 P{H} NMR spectroscopy together with single crystal X-ray diffraction studies.…”

“…The bonding mode of C 6 H 4 is a l 3 -benzyne ligand and is common for many other Ru/Os analogues known [6,17,19]. The alternating long and short CAC bond distances observed about the C 6 ring (benzyne) [C(13A)AC(14A) = 1.414 (6), C(14A)AC(15A) = 1.362 (8), C(15A)AC(16A) = 1.392 (8), C(16A)AC(17A) = 1.366(7), C(17A)AC(18A) = 1.423(7), C(13A)AC(18A) = 1.418(6) Å]. A similar benzyne bonding pattern is also observed in Os 3 (CO) 9 (l-CO) (l 3 -C 6 H 4 ) suggesting the occurrence of partial localizations in the p-bonding in the C6 ring induced by interruption in the delocalization of the p-bonding at the C(13)AC (18) bond which is also due to the coordination of these atoms to the Ru atoms [19].…”

“…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]. The cleavage of PAC or CAH bonds on the ligands are reported to cause the deactivation in homogeneous transition metal catalyst [9].…”

“…The cleavage of PAC or CAH bonds on the ligands are reported to cause the deactivation in homogeneous transition metal catalyst [9]. The thermolysis of Ru 3 (CO) 10 (dppm) in refluxing cyclohexane affords Ru 3 (CO) 9 [l 3 -PhPCH 2 PPh(C 6 H 4 )] as a result of one aryl CAP and one CAH cleavage [5,10] while the thermolysis of Os 3 (CO) 10 (dppm) in refluxing toluene yields unsaturated Os 3 (CO) 8 (CO) 10 (dppe) in refluxing toluene yields Ru 4 (CO) 9 (l-CO){l 4 -g 2 -PCH 2 CH 2 P(Ph) 2 }(l 4 -g 4 -C 6 H 4 )] [12]. Thus, the nuclearity of the cluster is preserved in products of Ru 3 (CO) 10 (dppm) while in Ru 3 (CO) 10 (dppe), there is a formation of tetranuclear complex.…”

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)

“…This σ,π-π,σ exchange is akin to the windshield-wiper process displayed by the metalated thienyl ligand in Ru 3 (CO) 7 (µ-dppf){µ 3 -(C 4 H 3 S) 2 P(C 4 H 2 S)}. 44 …”