Chiral hexarhodium carbonyl clusters containing heterobidentate phosphine ligands; a structural and reactivity study

Tunik, Sergey P.; Koshevoy, Igor O.; Poë, Anthony J.; Farrar, David H.; Nordlander, Ebbe; Haukka, Matti; Pakkanen, Tapani A.

doi:10.1039/b300951c

Cited by 46 publications

(55 citation statements)

References 59 publications

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“…The µ-(P,S) coordination mode has been detected for a diphenyl(2-benzothienyl)phosphane derivative of [Os 3 (CO) 12 ] [44] as well as in thienylphosphane derivatives of [Rh 6 (CO) 16 ]. [45] The fourth product, compound 8, was isolated in 3 % yield. The mass spectrum of this compound indicates that it has one more carbonyl ligand than compound 7. .…”

Section: Thermal Treatment Of [H 2 Os 3 (Co) 10 ] With Ph 2 P(c 4 H 3 S)mentioning

confidence: 99%

Syntheses and Fluxional Processes of Diphenyl(2‐thienyl)phosphane Derivatives of Triosmium Clusters

et al. 2006

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Thermal treatment of [Os3(CO)12] with diphenyl(2‐thienyl)phosphane, Ph2P(C4H3S), results in the formation of [Os3(CO)12–x{Ph2P(C4H3S)}x] (x = 1–3, 1–3), but no C–H bond activation was observed. Reaction of [H2Os3(CO)10] with diphenyl(2‐thienyl)phosphane at ambient temperature affords [HOs3(μ‐H)(CO)10{Ph2P(C4H3S)}] (4), but when the samereaction is repeated at elevated temperatures, the cyclometallated species [(μ‐H)Os3(CO)9{μ3‐Ph2P(C4H2S)}] (5) and[(μ‐H)Os3(CO)8{μ3‐Ph2P(C4H2S)}{Ph2P(C4H3S)}] (6) are formed. In addition, two more products, tentatively assigned as [(μ‐H)Os3(CO)6{μ3‐Ph2P(C4H2S)}{μ‐Ph2P(C4H3S)}{Ph2P(C4H3S)}] (7) and [(μ‐H)Os3(CO)7{μ‐Ph2P(C4H2S)}{μ‐Ph2P(C4H3S)}{Ph2P(C4H3S)}] (8) are obtained. The dynamic behaviours of 2, 5 and 6 have been studied by variable‐temperature (VT) 1H and 31P{1H} NMR spectroscopy. The VT 31P{1H} NMR spectra of [Os3(CO)10{Ph2P(C4H3S)}2] (2) demonstrate that a mixture of two isomers, which are in rapid exchange at room temperature, is present and that the less common cis‐trans isomer, whose structure has been determined by X‐ray crystallography, is favoured for this cluster. The VT 1H NMR spectra of 5 indicate the presence of two isomers which are proposed to arise from an oscillation of the σ,η2‐vinyl group of the thienyl moiety between two metal atoms. A similar fluxional process is proposed to occur in 6 and the assignment of the room‐temperature structure(s) of this cluster was confirmed by 1H‐187Os 2D HMQC spectroscopy. In addition to 2, the solid‐state structures of 3, 5 and 6 have been determined by X‐ray crystallography. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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Section: Thermal Treatment Of [H 2 Os 3 (Co) 10 ] With Ph 2 P(c 4 H 3 S)mentioning

confidence: 99%

Syntheses and Fluxional Processes of Diphenyl(2‐thienyl)phosphane Derivatives of Triosmium Clusters

et al. 2006

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“…The 1 H NMR spectrum in the aromatic region exhibits a set of multi plets typical of the terminally (through the phosphorus atom) coordinated ligand. 41 The molecular structure of compound 1 determined by the X ray diffraction method is shown in Fig. 1, and selected bond lengths and bond angles are given in Table 2.…”

Section: Synthesis Structure and Dynamic Behavior Of The Hydride LImentioning

confidence: 99%

Structure and dynamic properties of substituted carbonylhydride clusters H2RuOs3(CO)13 and H4Ru4(CO)12 containing functionalized phosphines

et al. 2007

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The derivatives of the H 2 RuOs 3 (CO) 13 and H 4 Ru 4 (CO) 12 carbonylhydride clusters con taining functionalized (including chiral) phosphines were synthesized. The solid state struc ture of H 2 RuOs 3 (CO) 12 (Ph 2 P(C 4 H 3 S)) was determined by X ray diffraction analysis. The structures of other compounds in solution were determined using IR and 1 H and 31 P NMR spectroscopy. A study of the temperature dependences of the 1 H NMR spectra of the phos phine substituted tetrahedral clusters along with the analysis of literature data for their analogs showed that compounds of this type exist in solution as an equilibrium mixture of isomers, which differ in arrangement of the hydride ligands at the cluster skeleton. Interconversion of the isomeric forms is due to migration of the hydride ligands over the cluster skeleton. A general model for this dynamic process was proposed. The model is consistent with both our data and earlier results of other authors.Carbonylhydride clusters of the iron subgroup transi tion metals are used as efficient catalysts in hydrogena tion of unsaturated organic compounds. 1-4 From this point of view, it seems most attractive to consider phos phine substituted derivatives of the H 4 Ru 4 (CO) 12 and H 2 RuOs 3 (CO) 12 clusters, whose activity in various or ganic reactions is well known. 1-14 Reactions of asymmet ric synthesis 15 are especially interesting from the theoreti cal and applied viewpoints, and reactions of this type catalyzed by cluster compounds have been most poorly studied up to date, and only restricted examples of using the clusters in asymmetrical catalysis are available in the literature. 16-18As a rule, in the organometallic complexes of this type the hydride ligands participate in the low barrier dynamic processes, such as hydride migration over the cluster skeleton in solution 19-24 and even in the solid phase. 25-27 The fast intramolecular hydride exchange in the cluster compounds in solution has been evidenced for the first time for a series of compounds H 4 Ru 4 (CO) 12-x L x (L = P(OMe 3 ), x = 1-4). 28 However, subsequent more detailed studies 22,29 of the structure of the ligand environment and mechanism of dynamic processes in these compounds revealed no general pattern, and some conclusions of the above cited works even contradict each other.In this work, we synthesized new tetrahedral mono substituted carbonylhydride clusters with functional ized phosphine ligands H 2 RuOs 3 (CO) 12 (PS) (1) and H 4 Ru 4 (CO) 11 L (2-5), where L = POx (2), PSug (3), PInd (4), and PStyr (5); PS is thienyldiphenylphosphine, POx is (1R,9R)[2(oxymethylquinolisidinyl)ethyl]di(2 phenylethyl)phosphine, PSug is (2 [5 (2,2 dimethyl 1,3 dioxolan 4 yl) 2,2 dimethyltetrahydrofuro[2,3 d][1,3]di oxol 6 yl]oxyethyl)di(2 phenylethyl)phosphine, PInd is [2 (1 indolyl)propyl]di(2 phenylethyl)phosphine, PStyr is (2 phenylpropyl)distyrylphosphine. The structures of compounds 1-5 in solution were studied, and a model for the dynamic behavior of their coordination sphere was proposed.

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“…4-6 Moreover, the stereochemical features of the structures of polynuclear complexes containing bridging heterobidentate ligands XY (these structural fragments can be formed only in polynuclear complexes) imply at tractive opportunities of using them in asymmetric syn thesis. 6,7 This review is devoted to some aspects of the synthesis and reactivity of the transition metal carbonyl clusters containing labile and hemilabile ligands, which are either widely used in fundamental research or are promising for practical application. The review does not claim to be exhaustive, being largely based on the results obtained by author´s research group during the last 10 years.…”

Section: Introductionmentioning

confidence: 99%

The chemistry of carbonyl clusters of transition metals containing labile and hemilabile ligands. Synthesis, reactivity, and prospects for application

Tunik

2004

Russ Chem Bull

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Chiral hexarhodium carbonyl clusters containing heterobidentate phosphine ligands; a structural and reactivity study

Cited by 46 publications

References 59 publications

Syntheses and Fluxional Processes of Diphenyl(2‐thienyl)phosphane Derivatives of Triosmium Clusters

Syntheses and Fluxional Processes of Diphenyl(2‐thienyl)phosphane Derivatives of Triosmium Clusters

Structure and dynamic properties of substituted carbonylhydride clusters H2RuOs3(CO)13 and H4Ru4(CO)12 containing functionalized phosphines

The chemistry of carbonyl clusters of transition metals containing labile and hemilabile ligands. Synthesis, reactivity, and prospects for application

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