P-C and C-H bond cleavages of dppm in the thermal reaction of [RU3(CO)10(μ-dppm)] with benzothiophene:: X-ray structures of [RU6(μ-CO)(CO)13{μ4-PhP(C6H4)PPh}(μ6-C)] and [RU4(CO)9(μ3-η2-PhPCH2PPh2)(μ4-η6:η1:η1-C6H4)(μ-H)]

Title full: P-C and C-H bond cleavages of dppm in the thermal reaction of [Ru3(CO)10(μ-dppm)] with benzothiophene: X-ray structures of [Ru6(μ-CO)(CO)13{μ4 -PhP(C6H4)PPh}(μ6-C)] and [Ru4(CO)9(μ3-η2-PhPCH 2PPh2)(μ4-η6:η 1:η1-C6H4)(μ-H)]. The thermal reaction of [Ru3(CO)10(μ-dppm)] (1) with benzothiophene in refluxing toluene gives a complex mixture of products. These include the known compounds [Ru2(CO)6{μ-CH2PPh(C6 H4)PPh}] (2), [Ru2(CO)6{μ-C6H4PPh (CH2)PPh}] (3), [Ru3(CO)9{μ3-η3-(Ph)P CH2P(Ph)C6H4}] (4) and [Ru3(CO)10{μ-η2-PPh(CH 2)(C6H4)PPh}] (6), as well as the new clusters [Ru6(μ-CO)(CO)13{μ3-η 2-PhP(C6H4)PPh}(μ6-C)] (5) and [Ru4(CO)9(μ3-η2-PhPCH 2PPh2)(μ4-η6:η 1:η1-C6H4)(μ-H)] (7). The solid-state molecular structures of 5 and 7 were confirmed by single crystal X-ray analyses. Compound 5 consists of interesting example of a hexaruthenium interstitial carbido cluster having a tetradentate diphosphine ligand derived from the activation of P-C and C-H bonds of the dppm ligand in 1. The tetranuclear compound 7 consists of a unique example of a non-planar spiked triangular metal fragment of ruthenium [Ru(1), Ru(2) and Ru(3)] unit with Ru(4) being bonded to Ru(1). The μ4-η1:η6:η1-b enzyne ligand in this compound represents a previously uncharacterized bonding mode for benzyne. Compounds 5 and 7 do not contain any benzothiophene-derived ligand. The reaction of 4 with benzothiophene gives 2, 3, 5 and 6. Thermolysis of 1 in refluxing toluene gives 2, 3 and 4; none of 5 and 7 is detected in reaction mixture. © 2007 Elsevier B.V. All rights reserved.