Reactivity of the Unsaturated Triosmium Cluster Os<sub>3</sub>(CO)<sub>8</sub>(μ<sub>3</sub>-η<sup>2</sup>-Ph<sub>2</sub>PCH<sub>2</sub>P(Ph)C<sub>6</sub>H<sub>4</sub>)(μ-H) with Benzothiophene: Activation of a P−C Bond in Diphosphine and a C−H Bond in Benzothiophene
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Treatment of the electronically unsaturated cluster Os3(CO)8(μ3-η2-Ph2PCH2P(Ph)C6H4)(μ-H) (1) with benzothiophene in refluxing m-xylene afforded Os3(CO)7(μ-PPh2)(μ-PMePh)(μ3-η2-C6H4) (2), Os3(CO)7(μ3-η2-PPh(C6H4)CH2PPh)(μ3-η3-SC8H5)(μ-H) (3), and Os3(CO)8(μ-CO)(μ3-η2-PPh(C6H4)CH2PPh) (4). Thermolysis of 1 in refluxing toluene for 35 h afforded only 4, whereas in refluxing m-xylene it gave both 4 and 2. Compound 4 can also be obtained from the thermolysis of Os3(CO)9(μ3-η2-PPh(C6H4)CH2PPh2)(μ-H) (5) in refluxing toluene. All the complexes have been structurally characterized. Compound 3 contains a unique example of a μ3-η2 benzothienyl ligand coordinated through the sulfur atom and the C−C double bond of the five-membered ring in a σ,π vinyl fashion. This coordination mode results in the rupture of one osmium−osmium bond, whereas the basic triangular metal framework is retained in the case of 2 and 4, which are derived from the activation of P−C and C−H bonds of 1 and do not contain any benzothiophene-derived ligand.
