Influence of the Diphosphine Coordinated to Molybdenum and Tungsten Triangular M3S4 Cluster Hydrides in the Catalytic Hydrodefluorination of Pentafluoropyridine

Alfonso, Carmina; Beltrán, Tomás F.; Feliz, Miguel; Llusar, Rosa

doi:10.1007/s10876-014-0733-1

Cited by 14 publications

(9 citation statements)

References 32 publications

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“…Hidai has provided several accounts on the mixed-metal sulfide cubane-type cluster [MMo3S4] as catalyst precursors for various transformation of alkynes (104,132,142,144), olefins (1d, 157), and hydrazines (46). For example, [PdMo3S4(H2O)9Cl]Cl3 (133) and [PdMo3S4(tacn)3Cl]Cl3 (134), tacn = 1,4,7-triazacyclononane, cubane-type clusters were found to be highly regioselective towards trans-addition of alcohols to alkynoic acid esters 132 leading to 135, Table 29 [162].…”

Section: Addition Reactionsmentioning

confidence: 99%

“…Mechanistic accounts were rationalized from DFT studies suggesting an initial phosphine dissociation from the cluster permitting M-H/C-F σ-bond metathesis. This compound, in turn, undergoes M-F/Si-H σ-bond metathesis that is concluded by re-coordination of the phosphine ligand as shown in Scheme To assess the influence of the phosphine ligands on catalytic activity, Llusar reported in a later study the activity of the dppe congeners, [M3S4H3(dppe)3] + , M = Mo (15f), W (93b)[132]. Approximately 90% yield was achieved at a significantly lower temperature (115 vs. 180 °C) and catalyst loading (0.7 vs. 1.0 mol%, respectively).…”

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confidence: 99%

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Homogeneous Catalysis by Organometallic Polynuclear Clusters

2019

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Homogeneous polynuclear metal clusters constitute a broad class of coordination compounds with important applications in catalysis. The current interest of synthetic chemistry in this field demands the exploration of new strategies to develop catalytic methods that work under mild conditions and maximize atom utilization. This review covers the application of polynuclear clusters of nuclearity ≥3 in homogeneous catalytic processes, with focus on providing an array of examples of various reaction types within cluster catalysis.

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Section: Addition Reactionsmentioning

confidence: 99%

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confidence: 99%

Homogeneous Catalysis by Organometallic Polynuclear Clusters

2019

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“…The interatomic Mo-Mo and Mo-S distances follow the tendencies observed for other Mo 3 S 4 cluster compounds. 10,16,17 Each molybdenum atom in…”

Section: Synthesis and Structurementioning

confidence: 99%

C₃-symmetry Mo₃S₄ aminophosphino clusters combining three sources of stereogenicity: stereocontrol directed by hydrogen bond interactions and ligand configuration

et al. 2016

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A diastereoselective synthesis of proline containing aminophosphino cubane-type Mo3S4 clusters, (P)-[Mo3S4Cl3((1S,2R)-PPro)3]Cl (Cl) and (P)-[Mo3S4Cl3((1S,2S)-PPro)3]Cl (Cl), has been achieved in high yields by reacting the corresponding enantiomerically pure PPro ((R)- and (S)-2-[(diphenylphosphino)methyl]pyrrolidine) ligands with the Mo3S4Cl4(PPh3)3(H2O)2 complex. Circular dichroism, nuclear magnetic resonance and X-ray techniques confirm that the Cl and Cl cluster cations are diastereoisomers which combine three sources of stereogenicity provided by the cluster framework, one carbon atom of the aminophosphine ligand and the nitrogen stereogenic center. The higher stability of the (+) cation is due to stabilizing vicinal ClHN interactions as well as due to the cis-fused conformation of the bicyclic system formed upon coordination of the aminophosphine ligand.

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“…In collaboration with the Beller group, some of us have recently investigated the catalytic performances of Mo 3 S 4 complexes functionalized with diphosphine, diamine and diimine ligands in the hydrogenation and transfer hydrogenation of nitroarenes . Moreover, group‐six M 3 S 4 clusters also catalyze the selective hydrodefluorination of pentafluoropyridine at the para position with silanes as the hydrogen source , …”

Section: Introductionmentioning

confidence: 99%

Studies on the Reactivity of the [W₃S₄Br₃(edpp)₃]⁺ [edpp = (2‐aminoethyl)diphenylphosphine] Cluster Cation towards Bases: The Active Role of the Amino Group

et al. 2017

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Detailed studies through stopped‐flow 31P{1H} NMR spectroscopy and ESI‐MS were performed for the reactions of the [W3S4Br3(edpp)3]+ [edpp = (2‐aminoethyl)diphenylphosphine] cluster with bases such as NaOH and Et3N in acetonitrile. For the reaction with OH– ions, the study allowed the identification of hydroxo species and the development of a procedure for the synthesis of the [W3S4(OH)3(edpp)3]+ cluster in high yields. This involves the substitution of the coordinated bromide ligands by OH– ligands, and the associated kinetics is several orders of magnitude faster than those with Cl–, F– and SCN– anions. The reactivity with Et3N is quite different and essentially leads to the formation of species resulting from proton abstraction at the NH2 groups of the edpp ligands, and the amine acts as a base. DFT calculations provided a rationalization of the experimental findings by showing that Et3N coordination does not occur even in the presence of a vacant coordination site. The computed pKa values for the different species involved in these reactions indicate the possibility of proton exchange between the NH2 groups of edpp and Et3N, and this behaviour was confirmed by the NMR spectroscopy and ESI‐MS data. The formation of intermediate cluster species containing the conjugate base of edpp also facilitates bromide dissociation and, thus, provides a reaction pathway with a lower energy barrier that justifies the faster formation of [W3S4(OH)3(edpp)3]+ with respect to other [W3S4X3(edpp)3]+ (X = Cl, F, SCN) clusters.

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Influence of the Diphosphine Coordinated to Molybdenum and Tungsten Triangular M3S4 Cluster Hydrides in the Catalytic Hydrodefluorination of Pentafluoropyridine

Abstract: Abstract. Hydrido molybdenum and tungsten (IV) cluster cations of formula [M3S4H3(dppe)3] + (dppe = 1,2-(bis)dimethylphosphinoethane), + (M=Mo)

Cited by 14 publications

References 32 publications

Homogeneous Catalysis by Organometallic Polynuclear Clusters

Homogeneous Catalysis by Organometallic Polynuclear Clusters

C₃-symmetry Mo₃S₄ aminophosphino clusters combining three sources of stereogenicity: stereocontrol directed by hydrogen bond interactions and ligand configuration

Studies on the Reactivity of the [W₃S₄Br₃(edpp)₃]⁺ [edpp = (2‐aminoethyl)diphenylphosphine] Cluster Cation towards Bases: The Active Role of the Amino Group

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Influence of the Diphosphine Coordinated to Molybdenum and Tungsten Triangular M3S4 Cluster Hydrides in the Catalytic Hydrodefluorination of Pentafluoropyridine

Abstract: Abstract. Hydrido molybdenum and tungsten (IV) cluster cations of formula [M3S4H3(dppe)3] + (dppe = 1,2-(bis)dimethylphosphinoethane), + (M=Mo)

Cited by 14 publications

References 32 publications

Homogeneous Catalysis by Organometallic Polynuclear Clusters

Homogeneous Catalysis by Organometallic Polynuclear Clusters

C3-symmetry Mo3S4 aminophosphino clusters combining three sources of stereogenicity: stereocontrol directed by hydrogen bond interactions and ligand configuration

Studies on the Reactivity of the [W3S4Br3(edpp)3]+ [edpp = (2‐aminoethyl)diphenylphosphine] Cluster Cation towards Bases: The Active Role of the Amino Group

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C₃-symmetry Mo₃S₄ aminophosphino clusters combining three sources of stereogenicity: stereocontrol directed by hydrogen bond interactions and ligand configuration

Studies on the Reactivity of the [W₃S₄Br₃(edpp)₃]⁺ [edpp = (2‐aminoethyl)diphenylphosphine] Cluster Cation towards Bases: The Active Role of the Amino Group