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)]

Authors

Shariff E. Kabir, Jahangirnagar University
Mohammad R. Hassan, Jahangirnagar University
Daniel T. Haworth, Marquette UniversityFollow
Sergey V. Lindeman, Marquette UniversityFollow
Tasneem Siddiquee, University of Wisconsin - MilwaukeeFollow
Dennis W. Bennett, University of Wisconsin - MilwaukeeFollow

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)₉{μ₃-η³-(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)₁₃{μ₃-η²-PhP(C₆H₄)PPh}(μ₆-C)] (5) and [Ru₄(CO)₉(μ₃-η²-PhPCH₂PPh₂)(μ₄-η⁶:η¹: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-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

Accepted version. Journal of Organometallic Chemistry, Vol. 692, No. 18 (August 15, 2007): 3936-3943. DOI. © 2018 Elsevier B.V. Used with permission.

Recommended Citation

Kabir, Shariff E.; Hassan, Mohammad R.; Haworth, Daniel T.; Lindeman, Sergey V.; Siddiquee, Tasneem; and Bennett, Dennis W., "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)]" (2007). Chemistry Faculty Research and Publications. 628.
https://epublications.marquette.edu/chem_fac/628