Complexes with functional phosphines
Identifieur interne : 002A71 ( Istex/Checkpoint ); précédent : 002A70; suivant : 002A72Complexes with functional phosphines
Auteurs : Pierre Braunstein [France] ; Silverio Coco Cea [France] ; Michael I. Bruce [France] ; Brian W. Skelton [Australie] ; Allan H. White [Australie]Source :
- Journal of Organometallic Chemistry [ 0022-328X ] ; 1992.
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- KwdEn :
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Abstract
Abstract: Reactions of the ketophosphine Ph2PCH2C(O)Ph (PO) with [Ru3(CO)12] afford the derivatives [Ru3(CO)11(PO)] (1) and [Ru3(CO)10(PO)2] (4). In the presence of triphenylphosphiniminium acetate (PPN)(OAc), the former leads to the labile [Ru3(CO)10{μ-(P O)}] (2), in which the functional phosphine acts as a (P,O) bridging ligand, whereas thermal activation of either 1 or 4 results in PCH bond cleavage and formation of [Ru3(μ-H) [μ-η1(O):η2(P,O) -O( CPh) CHPPh2} (CO)9] (3) whose crystal structure reveals an unprecedented bonding mode for the phosphinoenolate ligand, its oxygen atom bridging the Ru(1)Ru(2) edge. Protonation of this complex occurs selectively at the enolato-carbon and [Ru3 (μ-H)(μ-Ph2PCH2C(O)Ph}(CO)10]BF4 (5) and [Ru3(μ-H)(μ-Ph2PCH2C(O)Ph}2(CO)8]BF4 (7) were characterized in which the PO ligand(s) bridge between two Ru centres.
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DOI: 10.1016/0022-328X(92)83137-7
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<front><div type="abstract" xml:lang="en">Abstract: Reactions of the ketophosphine Ph2PCH2C(O)Ph (PO) with [Ru3(CO)12] afford the derivatives [Ru3(CO)11(PO)] (1) and [Ru3(CO)10(PO)2] (4). In the presence of triphenylphosphiniminium acetate (PPN)(OAc), the former leads to the labile [Ru3(CO)10{μ-(P O)}] (2), in which the functional phosphine acts as a (P,O) bridging ligand, whereas thermal activation of either 1 or 4 results in PCH bond cleavage and formation of [Ru3(μ-H) [μ-η1(O):η2(P,O) -O( CPh) CHPPh2} (CO)9] (3) whose crystal structure reveals an unprecedented bonding mode for the phosphinoenolate ligand, its oxygen atom bridging the Ru(1)Ru(2) edge. Protonation of this complex occurs selectively at the enolato-carbon and [Ru3 (μ-H)(μ-Ph2PCH2C(O)Ph}(CO)10]BF4 (5) and [Ru3(μ-H)(μ-Ph2PCH2C(O)Ph}2(CO)8]BF4 (7) were characterized in which the PO ligand(s) bridge between two Ru centres.</div>
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