Molecular Design of Cyclopentadienyl Tantalum Sulfide Complexes

Gómez, Manuel; González-Pérez, Juan I.; Hernández-Prieto, Cristina; Martı́n, Avelino; Mena, Miguel; Santamarı́a, Cristina; Temprado, Manuel

doi:10.1021/acs.inorgchem.8b03563

Cited by 6 publications

(20 citation statements)

References 40 publications

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“…Our initial analysis aimed to elucidate the bonding situation for the dinuclear parent compounds 1–3 , the tetranuclear [Ta(η 5 -C 5 Me 5 )(μ 3 -S)] 4 ( 4 ), and [Ta 2 (η 5 -C 5 Me 5 ) 2 (H)Ph(μ-S)(μ 3 -S)] 2 ( 5 ). Similarly to our previous studies on the electronic configuration of dinuclear sulfide Ta(IV) species, , compounds 1–3 display a HOMO orbital consisting of a σ-bonding combination between the d orbitals of the tantalum atoms, proving a σ bond between the two Ta(IV) centers (see Figure S28). For the cube-type structure 4 , we could identify four occupied molecular orbitals (from HOMO to HOMO – 3) based on tantalum d-type orbitals, which is a clear indication of the oxidation state III of tantalum atoms.…”

Section: Results and Discussionsupporting

confidence: 79%

“…The bond distances from Ta1 to the carbon atoms of the η 5 -cyclohexadienyl fragment are in the range of 2.33(1)–2.51(1) Å, which is similar to the metrical parameters found for a related tantalum compound reported by Tilley, , in which a η 5 -cyclohexadienyl fragment, also generated by hydrogenation of a phenyl ring, interacts with a vicinal Ta atom. The distance between the two metal centers (2.988(2) Å) is slightly longer than those observed in the alkyl precursors [Ta(η 5 -C 5 Me 5 )R(μ-S)] 2 [R = Me 2.929(1) Å, Ph 2.918(1) Å], but still within the range for an intermetallic bonding interaction …”

Section: Results and Discussionmentioning

confidence: 77%

“…Aiming to investigate the influence of the alkyl fragment on the hydrogenation processes, we first extended the family of dinuclear tantalum sulfido complexes previously synthesized . Compounds [Ta(η 5 -C 5 Me 5 )R(μ-S)] 2 [R = n Bu ( 1 ) CH 2 Ph ( 2 ), p -MeC 6 H 4 CH 2 ( 3 )] were prepared by the reaction of the dimetallic chloride species [Ta(η 5 -C 5 Me 5 )Cl(μ-S)] 2 with the corresponding alkylating reagent, [MgR 2 (thf) 2 ] (R = CH 2 Ph, p -MeC 6 H 4 CH 2 ) or Li n Bu, at room temperature in toluene or hexane (Scheme ).…”

Section: Results and Discussionmentioning

confidence: 99%

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Reductive Hydrogenation of Sulfido-Bridged Tantalum Alkyl Complexes: A Mechanistic Insight

Carbó,

Gómez,

Hernández-Prieto

et al. 2023

Inorg. Chem.

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Hydrogenolysis of a series of alkyl sulfido-bridged tantalum(IV) dinuclear complexes [Ta(η 5 -C 5 Me 5 )R(μ-S)] 2 [R = Me, nBu (1), Et, CH 2 SiMe 3 , C 3 H 5 , Ph, CH 2 Ph (2), p-MeC 6 H 4 CH 2 (3)] has led quantitatively to the Ta(III) tetrametallic sulfide cluster [Ta(η 5 -C 5 Me 5 )(μ 3 -S)] 4 (4) along with the corresponding alkane. Mechanistic information for the formation of the unique low-valent tetrametallic compound 4 was gathered by hydrogenation of the phenyl-substituted precursor [Ta(η 5 -C 5 Me 5 )Ph(μ-S)] 2 , which proceeds through a stepwise hydrogenation process, disclosing the formation of the intermediate tetranuclear hydride sulfide [Ta 2 (η 5 -C 5 Me 5 ) 2 (H)Ph(μ-S)(μ 3 -S)] 2 (5). Extending our studies toward tantalum alkyl precursors containing functional groups susceptible to hydrogenation, such as the allyl-and benzylsubstituted compounds [Ta(η 5 -C 5 Me 5 )(η 3 -C 3 H 5 )(μ-S)] 2 and [Ta(η 5 -C 5 Me 5 )(CH 2 Ph)(μ-S)] 2 (2), enables alternative reaction pathways en route to the formation of 4. In the former case, the dimetallic system undergoes selective hydrogenation of the unsaturated allyl moiety, forming the asymmetric complex [{Ta(η 5 -C 5 Me 5 )(η 3 -C 3 H 5 )}(μ-S) 2 {Ta(η 5 -C 5 Me 5 )(C 3 H 7 )}] (6) with only one propyl fragment. Species 2, in addition to the hydrogenation of one benzyl fragment and concomitant toluene release, also undergoes partial hydrogenation and dearomatization of the phenyl ring on the vicinal benzyl unity to give a η 5 -cyclohexadienyl complex [Ta 2 (η 5 -C 5 Me 5 ) 2 (μ-CH 2 C 6 H 6 )(μ-S) 2 ] (7). The mechanistic implications of the latter hydrogenation process are discussed by means of DFT calculations.

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Section: Results and Discussionsupporting

confidence: 79%

Section: Results and Discussionmentioning

confidence: 77%

Section: Results and Discussionmentioning

confidence: 99%

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Reductive Hydrogenation of Sulfido-Bridged Tantalum Alkyl Complexes: A Mechanistic Insight

Carbó,

Gómez,

Hernández-Prieto

et al. 2023

Inorg. Chem.

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“…We have evaluated computationally the possible structural isomers for complexes 2 and 3, in which the pentamethylcyclopentadienyl rings can be placed in the trans-or cis-position relative to the [Ti2NO] core, in a similar manner to those found for the dinuclear tantalum complexes, [Ta2(η 5 -C5Me5)2R2(μ-S)2] ( R = Me, CH2Me), previously published in our research group 29 . Figure 6 shows the molecular structures of the two possible isomers for each complex and their relative free energies.…”

Section: Resultsmentioning

confidence: 99%

A Bridging bis-Allyl Titanium Complex: Mechanistic Insights into the Electronic Structure and Reactivity

et al. 2019

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Treatment of the dinuclear compound [{Ti( 5 -C5Me5)Cl2}2(-O)] with allylmagnesium chloride provides the formation of the allyltitanium(III) derivative [{Ti( 5 -C5Me5)(-C3H5)}2(-O)] (1), structurally identified by single-crystal X-ray analysis. Density functional theory (DFT) calculations confirm that the electronic structure of 1 is a singlet state, and the molecular orbital analysis, along with the short Ti-Ti distance, reveal the presence of a metal-metal single bond between the two Ti(III) centers.Complex 1 reacts rapidly with organic azides, RN3 (R = Ph, SiMe3), to yield the allyl -imido derivatives3)] along with molecular nitrogen release. Reaction of 2 and 3 with H2 leads to the -imido propyl species [{Ti( 5 -C5Me5)(CH2CH2CH3)}2(-NR)(-O)] [R = Ph(4), SiMe3(5)]. Theoretical calculations were used to gain insight into the hydrogenation mechanism of complex 3 and rationalize the lower reactivity of 2.Initially, the -imido bridging group in these complexes activates the H2 molecule via addition to the Ti-N bonds. Subsequently, the titanium hydride intermediates induce a change in hapticity of the allyl ligands, and the nucleophilic attack of hydride to the allyl groups leads to metallacyclopropane intermediates. Finally, the proton transfer from the amido group to the metallacyclopropane moieties afford the propyl complexes 4 and 5.

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“…When designing chemical systems that are inspired by biological assemblies and transition metal clusters, metal sulfide (MS) complexes have shown to be of tremendous value. [ 2 ] Lanthanide complexes have gained substantial interest for therapeutic applications. The lanthanides peculiar electron configuration endows them with a number of properties, including fluorescence and redox activity, which can be crucial for some medical treatments, such as contrast, antibacterial, and chemotherapeutic drugs.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, characterization, antibacterial, antioxidant activities, density functional theory, and molecular docking studies of new organic metal complexes and links to application of corrosion inhibitors

Ahmed

Ashmawy

Abbas

et al. 2023

Applied Organom Chemis

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The condensation reaction between 5‐amino‐1,3,4‐thiadiazole‐2‐thiol and 1,2‐dibromoethane to afford the ligand L was carried out in direct to obtain the desired organic ligand. New [Er(L)ClH2O]Cl2·3H2O, [Yb(L)(H2O)2]Cl3·4H2O, and [Ta(L)Cl2]Cl3·4H2O complexes have been prepared from (L) by reacting one mole from metal ions with one mole from L. In addition to their physical characteristics, they were described using spectroscopic techniques (infrared [IR], nuclear magnetic resonance [NMR], and UV–Vis), gas chromatography (GC)‐mass, and X‐ray powder diffraction. Further interpretation of complex structures was supported by measurements of molar conductivity, magnetic susceptibility, mole ratio, and thermodynamic investigations in addition to theoretical study through the use of density functional theory and characterization techniques. IR spectral data showed the mode of action of the neutral tetradentate L ligand and its coordination via two N‐amine and two S‐thiols. The octahedral geometry surrounding the central lanthanide ions was suggested by the magnetic moments, diffused reflectance, and spectral data. Molar conductivity results exposed that Yb(III) and Ta(V) chelates were 1:3 electrolytes and Er(III) chelate was 1:2 electrolyte. In addition, practically all the complexes demonstrated effective antimicrobial activity against Escherichia coli, Pseudomonas aeruginosa, Bacillus subtilis, and Staphylococcus aureus species, via inhibition zone diameters in 9–15 mm mg−1 range. However, neither Candida albicans nor Aspergillus flavus species were susceptible to their antifungal effects. Finally, molecular docking (MOE) experiments showed the significant binding affinity of the ligand and its complexes with several 6KOC, 6LU4, and 6LU4 protein receptors. Finally, it is important to emphasize that these complexes may be potential antioxidant agents according to the biochemical results. Electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization (PP) methods were accustomed to examine the corrosion inhibition of aluminum silicon alloys (AlSi) in 1 M HCl solution. Experimental measurements indicate that the thiadiazole ligand reduces the corrosion rate.

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Molecular Design of Cyclopentadienyl Tantalum Sulfide Complexes

Cited by 6 publications

References 40 publications

Reductive Hydrogenation of Sulfido-Bridged Tantalum Alkyl Complexes: A Mechanistic Insight

Reductive Hydrogenation of Sulfido-Bridged Tantalum Alkyl Complexes: A Mechanistic Insight

A Bridging bis-Allyl Titanium Complex: Mechanistic Insights into the Electronic Structure and Reactivity

Synthesis, characterization, antibacterial, antioxidant activities, density functional theory, and molecular docking studies of new organic metal complexes and links to application of corrosion inhibitors

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