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| Naji, M. |
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| Motta, Antonella |
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| Mohamed, Tarek |
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| Ertürk, Emre |
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| Taccardi, Nicola |
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| Petrov, R. H. | Madrid |
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| Azam, Siraj |
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| Ospanova, Alyiya |
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| Ali, M. A. |
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| Popa, V. |
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| Rančić, M. |
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| Azevedo, Nuno Monteiro |
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Rennie, Moira A.
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article
Regiospecificity in reactions of alkynes and phosphines with the phosphido-bridged iron-cobalt complex [(OC)4Fe(μ-PPh2)Co(CO)3]
Abstract
<p>The iron-cobalt phosphido-bridged complex [(OC)<sub>4</sub>Fe(μ-PPh<sub>2</sub>)Co(CO)<sub>3</sub>] (1) can be prepared conveniently and in good yield from the reaction of [Co<sub>2</sub>(μ-PPh<sub>2</sub>)<sub>2</sub>(CO)<sub>6</sub>] with [Fe(CO)<sub>5</sub>]. A study of the reactivity of 1 towards symmetrical and unsymmetrical alkynes, R<sup>1</sup>CCR<sup>2</sup> (R<sup>1</sup>=R<sup>2</sup>=CO<sub>2</sub>Me, Ph; R<sup>1</sup>=H, R<sup>2</sup>=Ph), has been undertaken. In all cases, five-membered ferracycle-containing products of the type [(OC)<sub>3</sub>Fe{μ-PPh<sub>2</sub>C(O)CR<sup>1</sup>CR <sup>2</sup>}Co(CO)<sub>3</sub>] (R<sup>1</sup>=R<sup>2</sup>=CO<sub>2</sub>Me (2a), Ph (2c); R<sup>1</sup>=H, R<sup>2</sup>=Ph (2b)), are initially obtained in which a molecule of CO and a molecule of R<sup>1</sup>CCR<sup>2</sup> have been inserted regiospecifically into a Co-P bond in 1. Decarbonylation of 2a occurs during its preparation or in low yield on its thermolysis to give the four-membered ferracyclic species [(OC)<sub>3</sub>Fe{μ-PPh<sub>2</sub>C(CO<sub>2</sub>Me)C(CO <sub>2</sub>Me)}Co(CO)<sub>3</sub>] (3a). Similar thermolysis of 2b results not only in the related decarbonylation product [(OC)<sub>3</sub>Fe(μ-PPh<sub>2</sub>CHCPh)Co(CO)<sub>3</sub>] (3b), but additionally in three other products all in low yield, namely the regioisomer of 3b, [(OC)<sub>3</sub>Fe(μ-PPh<sub>2</sub>CPhCH)Co(CO)<sub>3</sub>] (4b), the aldehyde-substituted complex [(OC)<sub>3</sub>Fe{μ-PPh<sub>2</sub>C(CHO)CPh}Co(CO)<sub>3</sub>] (5b) and the five-membered ferracycle-containing species [(OC)<sub>3</sub>Fe{μ-PPh<sub>2</sub>CHCPhC(O)}Co(CO)<sub>3</sub>] (6b). Treatment of 2a and 2b with PPhMe<sub>2</sub> and P(OMe)<sub>3</sub> results in substitution of an iron-bound carbonyl group to give, respectively, [(PhMe<sub>2</sub>P)(OC)<sub>2</sub>Fe{μ-PPh<sub>2</sub>C(O)C(CO <sub>2</sub>Me)C(CO<sub>2</sub>Me)}(μ-CO)Co(CO)<sub>2</sub>] (7a) and [{(MeO)<sub>3</sub>P}(OC)<sub>2</sub>Fe{μ-PPh <sub>2</sub>C(O)CHCPh}(μ-CO)Co(CO)<sub>2</sub>] (7b) in high yield. In contrast, substitution of a cobalt-bound carbonyl is achieved on reaction of 3a with PPhMe<sub>2</sub> or PPh<sub>2</sub>H to give [(OC)<sub>3</sub>Fe{μ-PPh<sub>2</sub>C(CO<sub>2</sub>Me)C(CO <sub>2</sub>Me)}Co(CO)<sub>2</sub>(L)] (L=PPhMe<sub>2</sub> (8a), PPh<sub>2</sub>H (9a)). Thermolysis of the secondary phosphine-substituted complex 9a results in phosphorus-hydrogen bond cleavage to give [(OC)<sub>3</sub>Fe{μ-PPh<sub>2</sub>C(CO<sub>2</sub>Me)CH(CO <sub>2</sub>Me)}(μ-PPh<sub>2</sub>)Co(CO)<sub>2</sub>] (10a). Single-crystal X-ray diffraction studies have been performed on complexes 7b, 8a and 10a.</p>