Influence of the Ligand Alkyl Chain Length on the Solubility, Aqueous Speciation, and Kinetics of Substitution Reactions of Water- Soluble M3S4 (M = Mo, W) Clusters Bearing Hydroxyalkyl Diphosphines

Water-soluble [M3S4X3(dhbupe)3]+ diphosphino complexes (dhbupe = 1,2-bis(bis(hydroxybutyl)phosphino)ethane), 1+ (M = Mo, X = Cl) and 2+ (M = W; X = Br), have been synthesized by extending the procedure used for the preparation of their hydroxypropyl analogues by reaction of the M3S4(PPh3)3X4(solvent)x molecular clusters with the corresponding 1,2-bis- (bishydroxyalkyl)diphosphine. The solid state structure of the [M3S4X3(dhbupe)3]+ cation possesses a C3 symmetry with a cuboidal M3S4 unit, and the outer positions are occupied by one halogen and two phosphorus atoms of the diphosphine ligand. At a basic pH, the halide ligands are substituted by hydroxo groups to afford the corresponding [Mo3S4(OH)3(dhbupe)3]+ (1OH +) and [W3S4(OH)3(dhbupe)3]+ (2OH +) complexes. This behavior is similar to that found in 1,2-bis(bis(hydroxymethyl)phosphino)ethane (dhmpe) complexes and differs from that observed for 1,2-bis(bis(hydroxypropyl)phosphino)ethane (dhprpe) derivatives. In the latter case, an alkylhydroxo group of the functionalized diphosphine replaces the chlorine ligands to afford Mo3S4 complexes in which the deprotonated dhprpe acts in a tridentate fashion. Detailed studies based on stopped-flow, 31P{1H} NMR, and electrospray ionization mass spectrometry techniques have been carried out in order to understand the solution behavior and kinetics of interconversion between the different species formed in solution: 1 and 1OH + or 2 and 2OH +. On the basis of the kinetic results, a mechanism with two parallel reaction pathways involving water and OH− attacks is proposed for the formal substitution of halides by hydroxo ligands. On the other hand, reaction of the hydroxo clusters with HX acids occurs with protonation of the OH− ligands followed by substitution of coordinated water by X−

Combined kinetic and DFT studies on the stabilization of the pyramidal form of H3PO2 at the heterometal site of [Mo3M’S4(H2O)10]4+ clusters (M’= Pd, Ni)

Kinetic and DFT studies have been carried out on the reaction of the [Mo3M’S4(H2O)10]4+ clusters (M’= Pd, Ni) with H3PO2 to form the [Mo3M’(pyr-H3PO2)S4(H2O)9]4+ complexes, in which the rare pyramidal form of H3PO2 is stabilized by coordination to the M’ site of the clusters. The reaction proceeds with biphasic kinetics, both steps showing a first order dependence with respect to H3PO2. These results are interpreted in terms of a mechanism that involves an initial substitution step in which one tetrahedral H3PO2 molecule coordinates to M’ through the oxygen atom of the P=O bond, followed by a second step that consists in tautomerization of coordinated H3PO2 assisted by a second H3PO2 molecule. DFT studies have been carried out to obtain information on the details of both kinetic steps, the major finding being that the role of the additional H3PO2 molecule in the second step consists in catalysing a hydrogen shift from phosphorus to oxygen in O-coordinated H3PO2, which is made possible by its capability of accepting a proton from P-H to form H4PO2 + and then transfer it to the oxygen. DFT studies have been also carried out on the reaction at the Mo centres to understand the reasons that make these metal centres ineffective for promoting tautomerizatio

Fe(II) complexes of pyridine-substituted thiosemicarbazone ligands as catalysts for oxidations with hydrogen peroxide

La reacción de tres complejos [FeII(TSC)2], donde TSC es una ligando de tipo tiosemicarbazona sustituido por piridina, con H2O2 en acetonitrilo no permitía acumular los correspondientes complejos de Fe(III), [FeIII(TSC)2]+. En su lugar, se generaba una mezcla de especies de Fe(II) diamagnéticas de bajo espín. Según los espectros obtenidos por espectrometría de masas, estas especies eran el resultado de la adición secuencial de hasta cinco átomos de oxígeno al complejo. Esta capacidad para la adición de átomos de oxígeno sugirió que dichas especies podrían ser activas para la transferencia de átomos de oxígeno a sustratos externos. Por ello, se evaluó la capacidad de estos complejos para la oxidación de tioanisol y estireno empleando H2O2 como oxidante inicial. Los complejos fueron activos tanto en la oxidación de tioanisol a su sulfóxido como en la de estireno a benzaldehído, con escalas temporales que indicaban la participación de las especies intermedias que contenían los átomos de oxígeno añadidos. Curiosamente, los ligandos libres y el complejo [Zn(Dp44mT)2] también catalizaban la sulfoxidación selectiva del tioanisol, pero eran ineficaces para catalizar la oxidación del estireno a benzaldehído. Estos hallazgos abren nuevas vías para el desarrollo de catalizadores metálicos basados en tiosemicarbazonas en procesos de oxidación de gran interés

Benchmarking of DFTmethods using experimental free energies and volumes of activation for the cycloaddition of alkynes to cuboidalMo(3)S(4)clusters

Here, the kinetics of the concerted [3 + 2] cycloaddition reaction between the [Mo3(μ3‐S)(μ‐S)3Cl3(dmen)3]+ (dmen = N,N′‐dimethyl‐ethylenediamine) ([1]+) cluster and various alkynes to form dithiolene derivatives is thoroughly studied, with measurements at different temperatures and pressures allowing the determination of the free energies and volumes of activation. These parameters, together with the available single‐crystal X‐ray diffraction structures, are used to test a number of commonly used density functional theory (DFT) methods from Jacob's ladder, as well as the effects associated with the size of the basis sets, the way in which solvent effects are taken into account, or the inclusion of dispersion effects. Overall, a protocol that leads to average deviations between experimental and computed ΔV‡ and ΔG‡ values similar to the uncertainty of the experimental measurements is obtained

Benchmarking of DFT methods using experimental free energies and volumes of activation for the cycloaddition of alkynes to cuboidal Mo3S4 clusters

Here, the kinetics of the concerted [3 + 2] cycloaddition reaction between the [Mo3(μ3‐S)(μ‐S)3Cl3(dmen)3]+ (dmen = N,N′‐dimethyl‐ethylenediamine) ([1]+) cluster and various alkynes to form dithiolene derivatives is thoroughly studied, with measurements at different temperatures and pressures allowing the determination of the free energies and volumes of activation. These parameters, together with the available single‐crystal X‐ray diffraction structures, are used to test a number of commonly used density functional theory (DFT) methods from Jacob's ladder, as well as the effects associated with the size of the basis sets, the way in which solvent effects are taken into account, or the inclusion of dispersion effects. Overall, a protocol that leads to average deviations between experimental and computed ΔV and ΔG values similar to the uncertainty of the experimental measurements is obtained

Catalytic Hydrogenation of Azobenzene in the Presence of a Cuboidal Mo3S4 Cluster via an Uncommon Sulfur-Based H2 Activation Mechanism

Azobenzene hydrogenation is catalyzed under moderate conditions by a cuboidal Mo3(μ3-S)(μ-S)3 diamino complex via a cluster catalysis mechanism. Dihydrogen activation by the molecular [Mo3(μ3-S)(μ-S)3Cl3(dmen)3]+ cluster cation takes place at the μ-S bridging atoms without direct participation of the metals in clear contrast with classical concepts. The reaction occurs with the formation of 1,2-diphenylhydrazine as an intermediate with similar appearance and disappearance rate constants. On the basis of DFT calculations, a mechanism is proposed in which formation of 1,2-diphenylhydrazine and aniline occurs through two interconnected catalytic cycles that share a common reaction step that involves H2 addition to two of the bridging sulfur atoms of the catalyst to form a dithiolate Mo3(μ3-S)(μ-SH)2)(μ-S) adduct. Both catalytic cycles have similar activation barriers, in agreement with the experimental observation of close rate constant values. Microkinetic modeling of the process leads to computed concentration–time profiles in excellent agreement with the experimental ones providing additional support to the calculated reaction mechanism. Slight modifications on the experimental conditions of the catalytic protocol in combination with theoretical calculations discard a direct participation of the metal on the reaction mechanism. The effect of the ancillary ligands on the catalytic activity of the cluster fully agrees with the present mechanistic proposal. The results herein demonstrate the capability of molybdenum sulfide materials to activate hydrogen through an uncommon sulfur based mechanism opening attractive possibilities toward their applications as catalysts in other hydrogenation processes

Spin-Crossing in the (Z)-Selective Alkyne Semihydrogenation Mechanism Catalyzed by Mo3S4 Clusters: A Density Functional Theory Exploration

Semihydrogenation of internal alkynes catalyzed by the air-stable imidazolyl amino [Mo3S4Cl3(ImNH2)3]+ cluster selectively affords the (Z)-alkene under soft conditions in excellent yields. Experimental results suggest a sulfur-based mechanism with the formation of a dithiolene adduct through interaction of the alkyne with the bridging sulfur atoms. However, computational studies indicate that this mechanism is unable to explain the experimental outcome: mild reaction conditions, excellent selectivity toward the (Z)-isomer, and complete deuteration of the vinylic positions in the presence of CD3OD and CH3OD. An alternative mechanism that explains the experimental results is proposed. The reaction begins with the hydrogenation of two of the Mo3(μ3-S)(μ-S)3 bridging sulfurs to yield a bis(hydrosulfide) intermediate that performs two sequential hydrogen atom transfers (HAT) from the S–H groups to the alkyne. The first HAT occurs with a spin change from singlet to triplet. After the second HAT, the singlet state is recovered. Although the dithiolene adduct is more stable than the hydrosulfide species, the large energy required for the subsequent H2 addition makes the system evolve via the second alternative pathway to selectively render the (Z)-alkene with a lower overall activation barrier.CRUE-Universitat Jaume

Base-Free Catalytic Hydrogen Production from Formic Acid Mediated by a Cubane-Type Mo3S4 Cluster Hydride

Formic acid (FA) dehydrogenation is an attractive process in the implementation of a hydrogen economy. To make this process greener and less costly, the interest nowadays is moving toward non-noble metal catalysts and additive-free protocols. Efficient protocols using earth abundant first row transition metals, mostly iron, have been developed, but other metals, such as molybdenum, remain practically unexplored. Herein, we present the transformation of FA to form H2 and CO2 through a cluster catalysis mechanism mediated by a cuboidal [Mo3S4H3(dmpe)3]+ hydride cluster in the absence of base or any other additive. Our catalyst has proved to be more active and selective than the other molybdenum compounds reported to date for this purpose. Kinetic studies, reaction monitoring, and isolation of the [Mo3S4(OCHO)3(dmpe)3]+ formate reaction intermediate, in combination with DFT calculations, have allowed us to formulate an unambiguous mechanism of FA dehydrogenation. Kinetic studies indicate that the reaction at temperatures up to 60 °C ends at the triformate complex and occurs in a single kinetic step, which can be interpreted in terms of statistical kinetics at the three metal centers. The process starts with the formation of a dihydrogen-bonded species with Mo–H···HOOCH bonds, detected by NMR techniques, followed by hydrogen release and formate coordination. Whereas this process is favored at temperatures up to 60 °C, the subsequent β-hydride elimination that allows for the CO2 release and closes the catalytic cycle is only completed at higher temperatures. The cycle also operates starting from the [Mo3S4(OCHO)3(dmpe)3]+ formate intermediate, again with preservation of the cluster integrity, which adds our proposal to the list of the infrequent cluster catalysis reaction mechanisms.Funding for open access charge: CRUE-Universitat Jaume

Efficient (Z)-selective semihydrogenation of alkynes catalyzed by air-stable imidazolyl amino molybdenum cluster sulfides

Imidazolyl amino cuboidal Mo3(μ3-S)(μ-S)3 clusters have been investigated as catalysts for the semihydrogenation of alkynes. For that purpose, three new air-stable cluster salts [Mo3S4Cl3(ImNH2)3]BF4 ([1]BF4), [Mo3S4Cl3(ImNH(CH3))3]BF4 ([2]BF4) and [Mo3S4Cl3(ImN(CH3)2)3]BF4 ([3]BF4) have been isolated in moderate to high yields and fully characterized. Crystal structures of complexes [1]PF6 and [2]Cl confirm the formation of a single isomer in which the nitrogen atoms of the three imidazolyl groups of the ligands are located trans to the capping sulfur atom which leaves the three bridging sulfur centers on one side of the trimetallic plane while the amino groups lie on the opposite side. Kinetic studies show that the cluster bridging sulfurs react with diphenylacetylene (dpa) in a reversible equilibrium to form the corresponding dithiolene adduct. Formation of this adduct is postulated as the first step in the catalytic semihydrogenation of alkynes mediated by molybdenum sulfides. These complexes catalyze the (Z)-selective semihydrogenation of diphenylacetylene (dpa) under hydrogen in the absence of any additives. The catalytic activity lowers sequentially upon replacement of the hydrogen atoms of the N–H2 moiety in 1+ without reaching inhibition. Mechanistic experiments support a sulfur centered mechanism without participation of the amino groups. Different diphenylacetylene derivatives are selectively hydrogenated using complex 1+ to their corresponding Z-alkenes in excellent yields. Extension of this protocol to 3,7,11,15-tetramethylhexadec-1-yn-3-ol, an essential intermediate for the production of vitamin E, affords the semihydrogenation product in very good yield

Hydrogen-ion driven molecular motions in Cu2+-complexes of a ditopic phenanthrolinophane ligand

One of the first kinetic evaluations of a metal ion interchange between the two coordination sites of a ditopic macrocycle is presented.Garcia-España Monsonis, Enrique, [email protected] ; Soriano Soto, Concepción, [email protected] ; Verdejo Viu, Begoña, [email protected]