Title

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)134-PhP(C6H4)PPh}(μ6-C)] and [Ru4(CO)932-PhPCH2PPh2)(μ4611-C6H4)(μ-H)]

Document Type

Article

Language

eng

Publication Date

8-15-2007

Publisher

Elsevier

Source Publication

Journal of Organometallic Chemistry

Source ISSN

0022-3263

Abstract

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(C6H4)PPh}] (2), [Ru2(CO)6{μ-C6H4PPh(CH2)PPh}] (3), [Ru3(CO)933-(Ph)PCH2P(Ph)C6H4}] (4) and [Ru3(CO)10{μ-η2-PPh(CH2)(C6H4)PPh}] (6), as well as the new clusters [Ru6(μ-CO)(CO)1332-PhP(C6H4)PPh}(μ6-C)] (5) and [Ru4(CO)932-PhPCH2PPh2)(μ4611-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 μ4161-benzyne 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.

Comments

Journal of Organometallic Chemistry, Vol. 692, No. 18 (August 15, 2007): 3936-3943. DOI.

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