6 research outputs found
Hemilability of phosphine-thioether ligands coordinated to trinuclear Mo3S4 cluster and its effect on hydrogenation catalysis
Ligand-exchange reactions of [Mo3S4(tu)8(H2O)]Cl44H2O (tu = thiourea) with
(PhCH2CH2)2PCH2CH2SR ligands, where R = Ph (PS1), pentyl (PS2) or Pr (PS3) afford new
complexes isolated as [Mo3S4Cl3(PS1)3]PF6 ([1]PF6), [Mo3S4Cl3(PS2)3]PF6 ([2]PF6) and
[Mo3S4Cl3(PS3)3]PF6 ([3]PF6) salts in 30-50% yields as the major reaction products. The crystal
structures of [1]PF6 and [2]PF6 were determined by X-ray diffraction (XRD) analysis. Each of
the three phosphine-thioether ligands is coordinated in a bidentate chelating mode to a different
molybdenum atom of the Mo3S4 trinuclear cluster, herewith all the phosphorus atoms of the
phosphino-thioether ligand are located trans to the capping sulfur (3-S). A second product that
forms in the reaction of [Mo3S4(tu)8(H2O)]Cl44H2O with PS1 corresponds to the neutral
[Mo3S4Cl4(PS1)2(PS1*)] complex. Its XRD analysis reveals both bidentate (PS1) and
monodentate (PS1*) coordinating modes of the same ligand. In the latter mode the phosphinethioether
is coordinated to a Mo atom only via the P atom. All compounds were characterized by
1H, 31P{1H} NMR, electrospray-ionization (ESI) mass spectrometry and cyclic voltammetry
(CV). Reactions of [1]PF6, [2]PF6 and [3]PF6 with an excess of Bu4NCl in CD2Cl2 were followed
by 31P{1H} NMR. The spectra indicate equilibrium between cationic [Mo3S4Cl3(PSn)3]
+
and
neutral [Mo3S4Cl4(PSn)2(PSn*)] (n = 1, 2) species. The equilibrium constants were determined
as 2.5 ± 0.2103
, 43 ± 2 Đ
-1
and 30 ± 2 Đ
-1
(at 25°C) for [1]PF6, [2]PF6 and [3]PF6, indicating
quantitative differences in hemilabile behavior of the phosphino-thioether ligands, depending on
the substituent at sulfur. Clusters [1]PF6, [2]PF6 and [3]PF6 were tested as catalysts in reduction
of nitrobenzene to aniline with Ph2SiH2 under mild conditions. Significant differencies in the
catalytic activity were observed, which can be attributed to different hemilabile behavior of the
PS1 and PS2/PS3 ligands
WS2/MoS2 Heterostructures through Thermal Treatment of MoS2 Layers Electrostatically Functionalized with W3S4 Molecular Clusters
The preparation of 2D stacked layers that combine flakes of different nature, gives rise to countless number of heterostructures where new band alignments, defined at the interfaces, control the electronic properties of the system. Among the large family of 2D/2D heterostructures, the one formed by the combination of the most common semiconducting transition metal dichalcogenides WS2/MoS2, has awaken great interest due to its photovoltaic and photoelectrochemical properties. Solution as well as dry physical methods have been developed to optimize the synthesis of these heterostructures. Here a suspension of negatively charged MoS2 flakes is mixed with a methanolic solution of a cationic W3S4-core cluster, giving rise to a homogeneous distribution of the clusters over the layers. In a second step, a calcination under N2 of this molecular/2D heterostructure leads to the formation of clean WS2/MoS2 heterostructures where the photoluminescence of both counterparts is quenched, proving an efficient interlayer coupling. Thus, this chemical method combines the advantages of a solution approach (simple, scalable and low-cost) with the good quality interfaces reached by using more complicated traditional physical methods
Cycloaddition of alkynes to diimino Mo3S4 cubane-type clusters: a combined experimental and theoretical approach
A heterocyclic ligand 4,40-di-tert-butyl-2,20-bipyridine (dbbpy) has been coordinated to the Mo3S4 cluster unit affording the complex [Mo3S4Cl3(dbbpy)3]+ ([1]+) in a one-step ligand-exchange protocol from [Mo3S4(tu)8(H2O)]Cl4 4H2O (tu = thiourea). The new cluster was isolated as [1]PF6 and [1]Cl salts in high yields and the crystal structure of the latter determined by X-ray analysis. The synthetic procedure was extended to tungsten to afford [W3S4Cl3(dbbpy)3]+ ([2]+). Kinetic and NMR studies show that [1]+ reacts with several alkynes to form dithiolene species via concerted [3+2] cycloaddition reactions whereas [2]+ remains inert under similar conditions. The different rates for the reactions of [1]+ are rationalised by computational (DFT) calculations, which show that the more electron-withdrawing the substituents of the alkyne the faster the reaction. The inertness of [2]+ is due to the endergonicity of its reactions, which feature DGr values systematically 5â7 kcal mol 1 more positive than for those of [1]+
WS2/MoS2 Heterostructures via Thermal Treatment of MoS2 Layers Electrostatically Functionalized with W3S4 Molecular Clusters
The preparation of 2D stacked layers that combine flakes of different nature, gives rise
to countless number of heterostructures where new band alignments, defined at the interfaces,
control the electronic properties of the system. Among the large family of 2D/2D heterostructures,
the one formed by the combination of the most common semiconducting transition metal
dichalcogenides WS2/MoS2, has awaken great interest due to its photovoltaic and
photoelectrochemical properties. Solution as well as dry physical methods have been developed
to optimize the synthesis of these heterostructures. Here a suspension of negatively charged MoS2
flakes is mixed with a methanolic solution of a cationic W3S4-core cluster, giving rise to a
homogeneous distribution of the clusters over the layers. In a second step, a calcination under N2
of this molecular/2D heterostructure leads to the formation of clean WS2/MoS2 heterostructures
where the photoluminescence of both counterparts is quenched, proving an efficient interlayer
coupling. Thus, this chemical method combines the advantages of a solution approach (simple,
scalable and low-cost) with the good quality interfaces reached by using more complicated
traditional physical methods
Hydrolysis of Element (White) Phosphorus under the Action of Heterometallic Cubane-Type Cluster {Mo<sub>3</sub>PdS<sub>4</sub>}
Reaction of heterometallic cubane-type cluster complexesâ[Mo3{Pd(dba)}S4Cl3(dbbpy)3]PF6, [Mo3{Pd(tu)}S4Cl3(dbbpy)3]Cl and [Mo3{Pd(dba)}S4(acac)3(py)3]PF6, where dbaâdibenzylideneacetone, dbbpyâ4,4âČ-di-tert-butyl-2,2âČ-bipyridine, tuâthiourea, acacâacetylacetonate, pyâpyridine, with white phosphorus (P4) in the presence of water leads to the formation of phosphorous acid H3PO3 as the major product. The crucial role of the Pd atom in the cluster core {Mo3PdS4} has been established in the hydrolytic activation of P4 molecule. The main intermediate of the process, the cluster complex [Mo3{PdP(OH)3}S4Cl3(dbbpy)3]+ with coordinated P(OH)3 molecule and phosphine PH3, have been detected by 31P NMR spectroscopy in the reaction mixture
Hydrolysis of Element (White) Phosphorus under the Action of Heterometallic Cubane-Type Cluster {Mo3PdS4}
Reaction of heterometallic cubane-type cluster complexes—[Mo3{Pd(dba)}S4Cl3(dbbpy)3]PF6, [Mo3{Pd(tu)}S4Cl3(dbbpy)3]Cl and [Mo3{Pd(dba)}S4(acac)3(py)3]PF6, where dba—dibenzylideneacetone, dbbpy—4,4′-di-tert-butyl-2,2′-bipyridine, tu—thiourea, acac—acetylacetonate, py—pyridine, with white phosphorus (P4) in the presence of water leads to the formation of phosphorous acid H3PO3 as the major product. The crucial role of the Pd atom in the cluster core {Mo3PdS4} has been established in the hydrolytic activation of P4 molecule. The main intermediate of the process, the cluster complex [Mo3{PdP(OH)3}S4Cl3(dbbpy)3]+ with coordinated P(OH)3 molecule and phosphine PH3, have been detected by 31P NMR spectroscopy in the reaction mixture