A new family of phosphido-bridged dinuclear ruthenium carbonyl complexes: synthesis of [Ru2(CO)6{µ-P(C(CH)3O)2}(µ-η1,η2-C(CH)3O)] and its reactivity towards terminal alkynes
“…For instance, the reactivity of PFu3 with dirhenium complexes, [Re2(CO)10−n(NCMe)n] (n = 0-2), has been reported by us couple of years ago where we found its behavior closely similar to that of PPh3 [9] . More recently, we demonstrated the reactivity of PFu3 with triosmium clusters [10] , [Os3(CO)10−n(NCMe)n] (n = 0-2) and [Os3(CO)10(μ-H)2], and observed that here its behavior is quite different from that observed with Ru3(CO)12 which was documented by Wong et al [11] . Thus while the trinuclear framework is always maintained with osmium, the PFu3 substituted triruthenium clusters [Ru3(CO)12−n(PFu3)n] (n = 1, 2) and [Ru3(CO)9(PFu3)3] afford the furenyl complexes [Ru2(CO)6(μ-PFu2)(μ-η 1 ,η 2 -C4H3O)] [11], [12] and [Ru2(CO)5(PFu3)(μ-PFu2)(μ-η 1 ,η 2 -C4H3O)] [12] , respectively on heating by both ruthenium-ruthenium and phosphorus-carbon bond scission.…”
Section: Introductionmentioning
confidence: 47%
“…More recently, we demonstrated the reactivity of PFu3 with triosmium clusters [10] , [Os3(CO)10−n(NCMe)n] (n = 0-2) and [Os3(CO)10(μ-H)2], and observed that here its behavior is quite different from that observed with Ru3(CO)12 which was documented by Wong et al [11] . Thus while the trinuclear framework is always maintained with osmium, the PFu3 substituted triruthenium clusters [Ru3(CO)12−n(PFu3)n] (n = 1, 2) and [Ru3(CO)9(PFu3)3] afford the furenyl complexes [Ru2(CO)6(μ-PFu2)(μ-η 1 ,η 2 -C4H3O)] [11], [12] and [Ru2(CO)5(PFu3)(μ-PFu2)(μ-η 1 ,η 2 -C4H3O)] [12] , respectively on heating by both ruthenium-ruthenium and phosphorus-carbon bond scission. The chemistry of these diruthenium complexes has been extensively studied in the following years [11], [12], [13] .…”
Section: Introductionmentioning
confidence: 47%
“…Thus while the trinuclear framework is always maintained with osmium, the PFu3 substituted triruthenium clusters [Ru3(CO)12−n(PFu3)n] (n = 1, 2) and [Ru3(CO)9(PFu3)3] afford the furenyl complexes [Ru2(CO)6(μ-PFu2)(μ-η 1 ,η 2 -C4H3O)] [11], [12] and [Ru2(CO)5(PFu3)(μ-PFu2)(μ-η 1 ,η 2 -C4H3O)] [12] , respectively on heating by both ruthenium-ruthenium and phosphorus-carbon bond scission. The chemistry of these diruthenium complexes has been extensively studied in the following years [11], [12], [13] . As a continuation of our previous work on the reactivity of PFu3 with transition metal carbonyl complexes, we have now investigated its reactivity with [Mn2(CO)10−n(NCMe)n] (n = 0-2) the results of which are the subject of this article.…”
“…For instance, the reactivity of PFu3 with dirhenium complexes, [Re2(CO)10−n(NCMe)n] (n = 0-2), has been reported by us couple of years ago where we found its behavior closely similar to that of PPh3 [9] . More recently, we demonstrated the reactivity of PFu3 with triosmium clusters [10] , [Os3(CO)10−n(NCMe)n] (n = 0-2) and [Os3(CO)10(μ-H)2], and observed that here its behavior is quite different from that observed with Ru3(CO)12 which was documented by Wong et al [11] . Thus while the trinuclear framework is always maintained with osmium, the PFu3 substituted triruthenium clusters [Ru3(CO)12−n(PFu3)n] (n = 1, 2) and [Ru3(CO)9(PFu3)3] afford the furenyl complexes [Ru2(CO)6(μ-PFu2)(μ-η 1 ,η 2 -C4H3O)] [11], [12] and [Ru2(CO)5(PFu3)(μ-PFu2)(μ-η 1 ,η 2 -C4H3O)] [12] , respectively on heating by both ruthenium-ruthenium and phosphorus-carbon bond scission.…”
Section: Introductionmentioning
confidence: 47%
“…More recently, we demonstrated the reactivity of PFu3 with triosmium clusters [10] , [Os3(CO)10−n(NCMe)n] (n = 0-2) and [Os3(CO)10(μ-H)2], and observed that here its behavior is quite different from that observed with Ru3(CO)12 which was documented by Wong et al [11] . Thus while the trinuclear framework is always maintained with osmium, the PFu3 substituted triruthenium clusters [Ru3(CO)12−n(PFu3)n] (n = 1, 2) and [Ru3(CO)9(PFu3)3] afford the furenyl complexes [Ru2(CO)6(μ-PFu2)(μ-η 1 ,η 2 -C4H3O)] [11], [12] and [Ru2(CO)5(PFu3)(μ-PFu2)(μ-η 1 ,η 2 -C4H3O)] [12] , respectively on heating by both ruthenium-ruthenium and phosphorus-carbon bond scission. The chemistry of these diruthenium complexes has been extensively studied in the following years [11], [12], [13] .…”
Section: Introductionmentioning
confidence: 47%
“…Thus while the trinuclear framework is always maintained with osmium, the PFu3 substituted triruthenium clusters [Ru3(CO)12−n(PFu3)n] (n = 1, 2) and [Ru3(CO)9(PFu3)3] afford the furenyl complexes [Ru2(CO)6(μ-PFu2)(μ-η 1 ,η 2 -C4H3O)] [11], [12] and [Ru2(CO)5(PFu3)(μ-PFu2)(μ-η 1 ,η 2 -C4H3O)] [12] , respectively on heating by both ruthenium-ruthenium and phosphorus-carbon bond scission. The chemistry of these diruthenium complexes has been extensively studied in the following years [11], [12], [13] . As a continuation of our previous work on the reactivity of PFu3 with transition metal carbonyl complexes, we have now investigated its reactivity with [Mn2(CO)10−n(NCMe)n] (n = 0-2) the results of which are the subject of this article.…”
“…Phosphorus ligands possess the ability to act as σ-donors and π-acceptors simultaneously, allowing the ligand to adapt to the electronic characteristics of a metallic centre (1). Transition-metal-containing phosphorus compounds have found use in numerous applications, ranging from catalysis (2)(3)(4)(5)(6)(7) to medicine (8)(9)(10). Phosphorus-31 nuclear magnetic resonance (NMR) spectroscopy is one of the most important techniques for characterizing such compounds (11), and therefore, understanding the origin of phosphorus chemical shifts and their relationship with molecular structure is essential.…”
The present study examines the quality of the restricted Hartree-Fock (RHF) ab initio, B3LYP hybrid density functional theory (DFT), and relativistic zeroth-order regular approximation (ZORA) DFT methods for the calculation of phosphorus chemical shift (CS) tensors in phosphine, phosphido, and phosphinidene transition-metal complexes. A detailed comparison of calculated and experimental 31 P CS tensors allows us to identify the characteristic advantages of each computational method. The results from B3LYP and ZORA-DFT calculations indicate that a double-ζ quality basis set reproduces experimental values of the principal components of the 31 P CS tensor in many of the phosphoruscontaining transition-metal complexes investigated, whereas the RHF method requires a triple-ζ doubly polarized basis set, yet fails in the case of the terminal phosphido group. Inclusion of the spin-orbit relativistic correction with the ZORA-DFT formalism requires a triple-ζ quality basis set to reproduce the experimental data. We demonstrate the merit of modern computational methods for investigating theoretically the effect of geometric variations upon the phosphorus CS tensor by systematically altering the W-P bond length and the W-P-C Me bond angle in W(CO) 5 (PMe 3 ). Additionally, a previously reported correlation, determined experimentally, relating the 31 P CS tensor to the Fe-P-Fe bond angle in a series of iron phosphido-bridging compounds, has been reproduced with calculations using the model compound Fe 2 (CO) 6 (µ 2 -PPh 2 )(µ 2 -Cl). The results presented demonstrate the value of modern computational techniques for obtaining a greater understanding of the relationship between phosphorus chemical shifts and molecular structure.Résumé : Dans le présent travail, on examine la qualité de la théorie de densité fonctionnelle hybride B3LYP (« DFT »), une méthode ab initio de Hartree-Fock restreinte (« RHF »), ainsi que les méthodes « DFT » relativistes d'approximation régulière d'ordre zéro (« ZORA ») pour le calcul des tenseurs des déplacements chimiques (DC) du phosphore dans les complexes de métaux de transition contenant des groupes phosphine, phosphido et phosphinidène. Une comparaison détaillée des tenseurs calculés et expérimentaux des DC du 31 P a permis d'identifier les avantages caractéristiques de chacune de ces méthodes de calcul. Les résultats obtenus par les calculs B3YLP et « ZORA-DFT » indiquent qu'un ensemble de base de qualité double-ζ permet de reproduire les valeurs expérimentales des principaux composants du tenseur du DC du 31 P de plusieurs des complexes étudiés de métaux de transition contenant du phosphore; par ailleurs, la méthode RHF qui nécessite un ensemble de base doublement polarisé triple-ζ ne donne même pas de bons résultats avec le groupe phosphido terminal. Pour pouvoir reproduire les résultats expérimentaux en incluant la correction relativiste spin-orbite dans le formalisme « ZORA-DFT », il est nécessaire d'utiliser un ensemble de base de qualité triple-ζ. On démontre les mérites des méthodes mod...
“…Complex 2 was subsequently converted to a bisphosphine complex 3 by the action of another equivalent of PPh 3 with concomitant release of CO. The latter complex underwent an intriguing fragmentation in the presence of Cs 2 CO 3 at 110 °C to furnish phosphido-bridged bisruthenium complex 4 , presumably via P−C bond cleavage of one of the phosphine ligands, followed by the loss of 1 equiv of benzene and double Ru−Ru bond cleavage. 5b, The byproduct was identified as an inseparable mixture of bishydride triruthenium cluster 5a and its C2 symmetrical isomer 5b , in which the nitrogen atoms of both pyridine rings are coordinated to the same ruthenium center. 1 Generation of ruthenium dimer 4 .…”
Direct and selective catalytic arylation of alpha-C-H bond in pyridine with iodobenzene was achieved in up to 70% yield. Phosphido-bridged bisruthenium complexes 6a and 6b arising from Ru3(CO)12 and PPh3 were identified as active catalysts. The formation of complexes 6a and 6b was investigated, a sequence of C-H and C-P bond cleavage, cluster fragmentation, and disproportionation was established, and the intermediate ruthenium complexes lying on this pathway were isolated and fully characterized.
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