Novel synthesis of two tert-butyl ketenyl phosphinidine ligands on atrinuclear ruthenium framework. X-Ray structure determination of [Ru3(μ-dppm)(CO)7{μ3-PC( CO)But}2]
“…The Ru(1)−Ru(2) distances in 3 and 4 [2.703(1) and 2.712(1) Å, respectively] are significantly shorter than the other metal−metal bonds [2.851(1)−2.909(1) Å] and can be formally regarded as double bonds. The structural features are analogous to those of the tetranuclear clusters of [M 4 (μ 4 -PPh) 2 (μ-CO)(CO) 10 ] (M = Ru, Fe), [Co 2 Fe 2 (μ 4 -PPh) 2 (μ-CO)(CO) 10 ], and, more recently, [Ru 4 {μ 4 -PC(CO)tBu} 2 (μ-CO)(CO) 10 ] 6b…”
Section: Resultsmentioning
confidence: 63%
“…The second phosphinidene unit, arising from the attack of CO on tBuC⋮P, caps a Ru 3 fragment with one open edge. The 31 P shift associated with this phosphorus atom (δ = 149 ppm) lies in the range of those observed in related, ‘open' [Ru 3 {(μ 3 -PC(CO)tBu} 2 ] clusters. 6c,d There is little difference observed between the Ru−P bonding distances of the two ligands. 1 Molecular structure of [Ru 4 (CO) 13 (μ 3 -PPh){μ 3 -PC(CO)tBu}] ( 2 ) (ellipsoids drawn at 50% probability level).…”
Section: Resultsmentioning
confidence: 70%
“…The uptake of a CO molecule by the coordinatively unsaturated C atom of the methylidyne yields the ketene ligand. The formation of a ketene-substituted μ n -phosphinidene ligand ( n = 3, 4) was first observed in the complex [RePt(CO) 8 (dppe){PC(CO)tBu}],6a and more recently, additional examples were reported with the closo -clusters [Ru 3 M{μ 4 -PC(CO)tBu} 2 (μ-CO)(CO) 10 ] (M = Ru, Fe) 6b and the nido -clusters [M 3 {μ 3 -PC(CO)tBu} 2 (CO) 9 ] (M = Ru, Os) 6c and [Ru 3 (μ-dppm)(CO) 7 {μ 3 -PC(CO)tBu} 2 ] 6d 1 Reaction of 1 with RC⋮P …”
Section: Resultsmentioning
confidence: 99%
“…Examples of facile P−C bond formation, alkyne oligomerization, and skeletal transformations have been documented details of the reactivity of these molecules on polymetallic surfaces are surprisingly scarce . The highly activated cluster 1 provides an opportunity to explore the chemistry of RC⋮P on cluster frames, and our findings are presented herein.…”
The 62-electron cluster [Ru 4 (CO) 13 (µ 3 -PPh)] (1) reacts with phosphalkynes RCtP [(R ) tBu, Ar′ (2,4,6-tBu 3 C 6 H 2 )] to yield a series of unsymmetrically capped bisphosphinidene clusters characterized by a ketene substituted µ 4 -PR ligand. The reaction pathway was followed by 31 P-NMR spectroscopy and reveals that, in the first step of the reaction, a CO substitution of 1 occurs in order to form an intermediate with a σ-or π-bonded phosphaalkyne. After scavenging of CO the chain compound [Ru 4 (CO) 12 (µ 3 -PPh)(µ 3 -PC(CO)R)] [R ) tBu (2), Ar′ ( 7)] is created. Further CO elimination leads to the closo-complexes [Ru 4 (CO) 10 (µ-CO)-(µ 4 -PPh)(µ 4 -PC(CO)R)] [R ) tBu (3), Ar′ (4)]. Due to steric reasons the nido-cluster [Ru 3 (CO) 9 (µ 3 -PPh){µ 3 -PC(CO)tBu}] (5) is the final product in the reaction starting from Ar′CtP. The molecular structures of the complexes 2-5 are discussed.1 provides an opportunity to explore the chemistry of RCtP on cluster frames, and our findings are presented herein.
Results and DiscussionThe reactions of [Ru 4 (CO) 13 (µ 3 -PPh)] (1) with different phosphaalkynes lead to various ketene ligand-containing clusters. The ligand tBuCtP reacts with 1 at ambient temperatures to yield the complex [Ru 4 (CO) 12 -(µ 3 -PPh)(µ 3 -PC(CO)tBu)] (2) (Scheme 1), whereas at 60 °C the closo-complex [Ru 4 (CO) 10 (µ-CO)(µ 4 -PPh)(µ 4 - † Dedicated to Professor W. Siebert on the occasion of his 60th birthday.
“…The Ru(1)−Ru(2) distances in 3 and 4 [2.703(1) and 2.712(1) Å, respectively] are significantly shorter than the other metal−metal bonds [2.851(1)−2.909(1) Å] and can be formally regarded as double bonds. The structural features are analogous to those of the tetranuclear clusters of [M 4 (μ 4 -PPh) 2 (μ-CO)(CO) 10 ] (M = Ru, Fe), [Co 2 Fe 2 (μ 4 -PPh) 2 (μ-CO)(CO) 10 ], and, more recently, [Ru 4 {μ 4 -PC(CO)tBu} 2 (μ-CO)(CO) 10 ] 6b…”
Section: Resultsmentioning
confidence: 63%
“…The second phosphinidene unit, arising from the attack of CO on tBuC⋮P, caps a Ru 3 fragment with one open edge. The 31 P shift associated with this phosphorus atom (δ = 149 ppm) lies in the range of those observed in related, ‘open' [Ru 3 {(μ 3 -PC(CO)tBu} 2 ] clusters. 6c,d There is little difference observed between the Ru−P bonding distances of the two ligands. 1 Molecular structure of [Ru 4 (CO) 13 (μ 3 -PPh){μ 3 -PC(CO)tBu}] ( 2 ) (ellipsoids drawn at 50% probability level).…”
Section: Resultsmentioning
confidence: 70%
“…The uptake of a CO molecule by the coordinatively unsaturated C atom of the methylidyne yields the ketene ligand. The formation of a ketene-substituted μ n -phosphinidene ligand ( n = 3, 4) was first observed in the complex [RePt(CO) 8 (dppe){PC(CO)tBu}],6a and more recently, additional examples were reported with the closo -clusters [Ru 3 M{μ 4 -PC(CO)tBu} 2 (μ-CO)(CO) 10 ] (M = Ru, Fe) 6b and the nido -clusters [M 3 {μ 3 -PC(CO)tBu} 2 (CO) 9 ] (M = Ru, Os) 6c and [Ru 3 (μ-dppm)(CO) 7 {μ 3 -PC(CO)tBu} 2 ] 6d 1 Reaction of 1 with RC⋮P …”
Section: Resultsmentioning
confidence: 99%
“…Examples of facile P−C bond formation, alkyne oligomerization, and skeletal transformations have been documented details of the reactivity of these molecules on polymetallic surfaces are surprisingly scarce . The highly activated cluster 1 provides an opportunity to explore the chemistry of RC⋮P on cluster frames, and our findings are presented herein.…”
The 62-electron cluster [Ru 4 (CO) 13 (µ 3 -PPh)] (1) reacts with phosphalkynes RCtP [(R ) tBu, Ar′ (2,4,6-tBu 3 C 6 H 2 )] to yield a series of unsymmetrically capped bisphosphinidene clusters characterized by a ketene substituted µ 4 -PR ligand. The reaction pathway was followed by 31 P-NMR spectroscopy and reveals that, in the first step of the reaction, a CO substitution of 1 occurs in order to form an intermediate with a σ-or π-bonded phosphaalkyne. After scavenging of CO the chain compound [Ru 4 (CO) 12 (µ 3 -PPh)(µ 3 -PC(CO)R)] [R ) tBu (2), Ar′ ( 7)] is created. Further CO elimination leads to the closo-complexes [Ru 4 (CO) 10 (µ-CO)-(µ 4 -PPh)(µ 4 -PC(CO)R)] [R ) tBu (3), Ar′ (4)]. Due to steric reasons the nido-cluster [Ru 3 (CO) 9 (µ 3 -PPh){µ 3 -PC(CO)tBu}] (5) is the final product in the reaction starting from Ar′CtP. The molecular structures of the complexes 2-5 are discussed.1 provides an opportunity to explore the chemistry of RCtP on cluster frames, and our findings are presented herein.
Results and DiscussionThe reactions of [Ru 4 (CO) 13 (µ 3 -PPh)] (1) with different phosphaalkynes lead to various ketene ligand-containing clusters. The ligand tBuCtP reacts with 1 at ambient temperatures to yield the complex [Ru 4 (CO) 12 -(µ 3 -PPh)(µ 3 -PC(CO)tBu)] (2) (Scheme 1), whereas at 60 °C the closo-complex [Ru 4 (CO) 10 (µ-CO)(µ 4 -PPh)(µ 4 - † Dedicated to Professor W. Siebert on the occasion of his 60th birthday.
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