Recent advances in the chemistry of tris(thiolato) bridged cyclopentadienyl dimolybdenum complexes

Pétillon, François Y.; Schollhammer, Philippe; Talarmin, Jean

doi:10.1016/j.ccr.2016.10.004

Cited by 16 publications

(24 citation statements)

References 195 publications

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“…To date, a large variety of metal thiolate complexes have been designed and synthesized, which were commonly used as biomimetic structural and functional models of some important metalloenzymes [2] or excellent catalysts for organic transformations [3] . In sharp contrast to the great number and structural diversity of iron, [4] molybdenum [5] and nickel thiolate complexes, [6] chromium thiolate complexes are only limited to a few systems, [7] especially binuclear framework [8] . However, chromium as a trace element in the life system plays important roles in maintaining proper carbohydrate and lipid metabolism [9] .…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, and Oxidative Reactivity of a Class of Thiolate‐Bridged Dichromium Complexes Featuring Antiferromagnetic Coupling Interactions

et al. 2021

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Several thiolate‐bridged dichromium complexes with Cp* (Cp*=η5‐C5Me5) as auxiliary ligands were designed and synthesized through the salt metathesis, which all contain two six‐coordinate chromium centers in the formal valence of +3. These complexes are all paramagnetic species, which are in good agreement with the experimental results that broad and paramagnetically shifted proton resonances appear in the 1H NMR spectra. Furthermore, variable‐temperature solid‐state magnetic susceptibility studies reveal the two chromium centers of these complexes are both in an S=3/2 high‐spin state with a strong antiferromagnetic coupling. Simulated values of antiferromagnetic coupling constant for these complexes are directly related to the distances of the two CrIII centers confirmed by X‐ray crystallography. In addition, in the presence of dehalogenation agent AgPF6, complexes [Cp*CrCl(μ‐SR)2CrClCp*] (3, R=Et; 4, R=iPr) and [Cp*Cr(μ‐Cl)(μ‐SEt)2CrCp*][BPh4] (5) containing easily removable chloride can achieve the catalytic oxidation of organic substrates, such as PPh3, 1,4‐cyclohexadiene and 1,2‐diphenylhydrazine under an oxygen atmosphere.

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Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, and Oxidative Reactivity of a Class of Thiolate‐Bridged Dichromium Complexes Featuring Antiferromagnetic Coupling Interactions

et al. 2021

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“…Iron complexes serve as carbon-halogen bond activation reagents, and carbon-halogen bond-cleavage agents, [1][2][3][4] while osmium 5 , iridium, rhodium [6][7][8][9][10][11][12] and especially ruthenium complexes 13,14,[23][24][25][15][16][17][18][19][20][21][22] have in vitro antiproliferative activity against cancer cell lines and several protozoan parasites. Tris(thiolato)-bridged dimolybdenum complexes are also readily available but are synthesised using other strategies such as the direct oxidation of low-valence carbonyl precursors or reductive process from higher-valence derivatives, [26][27][28] which will not be discussed here. It is interesting to note that arene ruthenium(II) complexes were first obtained fortuitously about fifty years ago by Winkhaus and Singer and subsequently Zelonka and Baird.…”

Section: Dinuclear Thiolato-bridged Arene Ruthenium Complexes: From Reaction Conditions and Mechanism To Synthesis Of New Complexes 1 Intmentioning

confidence: 99%

Synthetic Route of Trithiolato-Bridged Dinuclear Arene Ruthenium(II) Complexes [(η6-P-MeC6H4Pri)2Ru2(μ2-SR)3]+

Primasova¹,

Ninova²,

Furrer

et al. 2020

Preprint

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Several dinuclear thiophenolato-bridged arene ruthenium complexes [(η6-p-MeC6H4Pri)2Ru2(μ2-SC6H4-R)3]+ could so far only be obtained with moderate yields using the synthetic route established in the early 2000s. With much less reactive aliphatic thiols or with bulky thiols, the reactions become even less efficient and the desired complexes are obtained with low yields or not at all. We employed density functional theory (DFT) calculations to gain a fundamental understanding of the reaction mechanisms leading to the formation of dithiolato and trithiolato complexes starting from the dichloro(pcymene) ruthenium(II) dimer [(η6-p-MeC6H4Pri)Ru(μ2-Cl)Cl]2. The results of the DFT study enabled us to rationalise experimental results and allowed us, via a modified synthetic route, to synthesise previously unreported and hitherto considered as unrealistic complexes. Our study opens possibilities for the synthesis of so far inaccessible thiolato-bridged dinuclear arene ruthenium(II) complexes but more generally also the synthesis of other thiolato-bridged dinuclear group 8 and 9 metal complexes could be reexamined.

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“… 7 This is essentially due to the cooperative effects supplied by the two adjacent metal centers working in concert and the availability of bridging coordination sites enabling peculiar reactivity patterns. 8 , 9 Starting from the easily available and inexpensive [Fe 2 Cp 2 (CO) 4 ] (Cp = η 5 -C 5 H 5 ) and via the preliminary replacement of one CO (either by chemical or photochemical methods), it is possible to obtain a huge diversity of hydrocarbyl ligands. 7 , 10 Usually, the latter are firmly anchored to the two irons by means of bridging carbyne or carbene atoms, and their removal from coordination is hardly viable even at high temperatures.…”

Section: Introductionmentioning

confidence: 99%

Tetrasubstituted Selenophenes from the Stepwise Assembly of Molecular Fragments on a Diiron Frame and Final Cleavage of a Bridging Alkylidene

et al. 2020

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A series of 2,3-dicarboxylato-5-acetyl-4-aminoselenophenes, 5a – j , was obtained via the uncommon assembly of building blocks on a diiron platform, starting from commercial [Fe 2 Cp 2 (CO) 4 ] through the stepwise formation of diiron complexes [ 2a – d ]CF 3 SO 3 , 3a – d , and 4a – j . The selenophene-substituted bridging alkylidene ligand in 4a – j is removed from coordination upon treatment with water in air under mild conditions (ambient temperature in most cases), affording 5a – j in good to excellent yields. This process is highly selective and is accompanied by the disruption of the organometallic scaffold: cyclopentadiene (CpH) and lepidocrocite (γ-FeO(OH)) were identified by NMR and Raman analyses at the end of one representative reaction. The straightforward cleavage of the linkage between a bridging Fischer alkylidene and two (or more) metal centers, as observed here, is an unprecedented reaction in organometallic chemistry: in the present case, the carbene function is converted to a ketone which is incorporated into the organic product. DFT calculations and electrochemical experiments were carried out to give insight into the release of the selenophene-alkylidene ligand. Compounds 5a – j were fully characterized by elemental analysis, mass spectrometry, IR, and multinuclear NMR spectroscopy and by X-ray diffraction and cyclic voltammetry in one case.

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Recent advances in the chemistry of tris(thiolato) bridged cyclopentadienyl dimolybdenum complexes

Cited by 16 publications

References 195 publications

Synthesis, Structure, and Oxidative Reactivity of a Class of Thiolate‐Bridged Dichromium Complexes Featuring Antiferromagnetic Coupling Interactions

Synthesis, Structure, and Oxidative Reactivity of a Class of Thiolate‐Bridged Dichromium Complexes Featuring Antiferromagnetic Coupling Interactions

Synthetic Route of Trithiolato-Bridged Dinuclear Arene Ruthenium(II) Complexes [(η6-P-MeC6H4Pri)2Ru2(μ2-SR)3]+

Tetrasubstituted Selenophenes from the Stepwise Assembly of Molecular Fragments on a Diiron Frame and Final Cleavage of a Bridging Alkylidene

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