Introducing Benzene-1,3,5-tri(dithiocarboxylate) as a Multidentate Linker in Coordination Chemistry

Aust, Margit; Herold, A.; Niederegger, Lukas; Schneider, Christian; Mayer, David C.; Drees, Markus; Warnan, Julien; Pöthig, Alexander; Fischer, Roland A.

doi:10.1021/acs.inorgchem.1c03045

Cited by 3 publications

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“… A similar 13 C NMR experiment performed at −80 °C with 4.0 mM [K(THF) 3 ]·1 , and 2.3 equiv 13 CS 2 revealed a signal at 231.9 ppm, which is suggestive of the formation of a dithiocarboxylate (Figure S12). − …”

Section: Resultsmentioning

confidence: 99%

Metal-Tuned Ligand Reactivity Enables CX₂ (X = O, S) Homocoupling with Spectator Cu Centers

Ocampo,

Murray

2024

J. Am. Chem. Soc.

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Ligand non-innocence is ubiquitous in catalysis with ligands in synthetic complexes contributing as electron reservoirs or co-sites for substrate activation. The latter chemical non-innocence is manifested in H + storage or relay at sites beyond the metal primary coordination sphere. Reaction of a competent CO 2 -to-oxalate reduction catalyst, namely, [K(THF) 3 ](Cu 3 SL), where L 3− is a tris(β-diketiminate) cyclophane, with CS 2 affords tetrathiooxalate at long reaction times or at high CS 2 concentrations, where otherwise an equilibrium is established between the starting species and a complex−CS 2 adduct in which the CS 2 is bound to the C atom on the ligand backbone. X-ray diffraction analysis of this adduct reveals no apparent metal participation, suggesting an entirely ligand-based reaction controlled by the charge state of the cluster. Thermodynamic parameters for the formation of the aforementioned C ligand −CS 2 bond were experimentally determined, and trends with cation Lewis acidity were studied, where more acidic cations shift the equilibrium toward the adduct. Relevance of such an adduct in the reduction of CO 2 to oxalate by this complex is supported by DFT studies, similar effects of countercation Lewis acidity on product formation, and the homocoupled heterocumulene product speciation as determined by isotopic labeling studies. Taken together, this system extends chemical non-innocence beyond H + to effect catalytic transformations involving C−C bond formation and represents the rarest example of metal−ligand cooperativity, that is, spectator metal ion(s) and the ligand as the reaction center.

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Section: Resultsmentioning

confidence: 99%

Metal-Tuned Ligand Reactivity Enables CX₂ (X = O, S) Homocoupling with Spectator Cu Centers

Ocampo,

Murray

2024

J. Am. Chem. Soc.

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“…The sodium salt of the dithiocarboxylate linker Na 2 (BDDTC) was prepared according to a previously published procedure . Triflate metal precursors were purchased from STREM Chemicals Inc. (Fe(OTf) 2 ) and Sigma-Aldrich ((Zn(OTf) 2 and Mn(OTf) 2 ) and used as received.…”

Section: Methodsmentioning

confidence: 99%

“…The other example is the polymeric structure of sodium salt Na 2 BDDTC, which was reported by our group very recently. In this case, additional cross-linking via Na–S coordination can be observed, which results in an extended 2D sheet structure …”

Section: Introductionmentioning

confidence: 99%

“…In this case, additional cross-linking via Na−S coordination can be observed, which results in an extended 2D sheet structure. 35 Herein, we investigate a series of CPs built from three different transition metals coordinated by the ditopic B D D T C 2 − l i n k e r . T h e c r y s t a l l i n e m a t e r i a l s [Mn(BDDTC)(DMF) 2 ] (1), [Zn 2 (BDDTC) 3 ][Zn-(DMF) 5 H 2 O] (2), and [Fe 2 (BDDTC) 2 (OH)] (3) built with Mn, Zn, and Fe inorganic building units were obtained by solvothermal synthesis and subsequently characterized.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The sodium salt of the dithiocarboxylate linker Na 2 (BDDTC) was prepared according to a previously published procedure. 35 Triflate metal precursors were purchased from STREM Chemicals Inc. (Fe(OTf) 2 ) and Sigma-Aldrich ((Zn(OTf) 2 and Mn(OTf) 2 ) and used as received. Anhydrous MeOH and dimethylformamide (DMF) (Sigma-Aldrich) were degassed prior to use and stored in an argon-filled glovebox over activated molecular sieves (3 Å).…”

Section: ■ Introductionmentioning

confidence: 99%

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Benzene-1,4-Di(dithiocarboxylate) Linker-Based Coordination Polymers of Mn²⁺, Zn²⁺, and Mixed-Valence Fe^2+/3+

Aust,

Schönherr,

Halter

et al. 2023

Inorg. Chem.

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Three new coordination polymers (CPs) constructed from the linker 1,4-di(dithiocarboxylate) (BDDTC 2− )� the sulfur-analog of 1,4-benzenedicarboxylate (BDC 2− )�together with Mn-, Zn-, and Fe-based inorganic SBUs are reported with description of their structural and electronic properties. Singlecrystal X-ray diffraction revealed structural diversity ranging from one-dimensional chains in [Mn(BDDTC)(DMF) 2 ] (1) to twodimensional (2D) honeycomb sheets observed for [Zn 2 (BDDTC) 3 ][Zn(DMF) 5 (H 2 O)] (2). Gas adsorption experiments confirmed a 3D porous structure for the mixed-valent material [Fe 2 (BDDTC) 2 (OH)] (3). 3 contains a 1:1 ratio of Fe 2+/3+ ions, as evidenced by 57 Fe Mossbauer, X-band EPR, and X-ray absorption spectroscopy. Its empirical formula was established by elemental analysis, thermal gravimetric analysis, infrared vibrational spectroscopy, and X-ray absorption spectroscopy in lieu of elusive single-crystal X-ray diffraction data. In contrast to the Mn-and Zn-based compounds 1 and 2, the Fe 2+/3+ CP 3 showed remarkably high electrical conductivity of 5 × 10 −3 S cm −1 (according to van der Pauw measurements), which is within the range of semiconducting materials. Overall, our study confirms that sulfur derivatives of typical carboxylate linkers (e.g., BDC) are suitable for the construction of electrically conducting CPs, due to acceptedly higher covalency in metal−ligand bonding compared to the electrically insulating carboxylate CPs or metal-organic frameworks. At the same time, the direct comparison between insulating CPs 1 and 2 with CP 3 emphasizes that the electronic structure of the metal is likewise a crucial aspect to construct electrically conductive materials.

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Single stranded 1D-helical Cu coordination polymer for ultra-sensitive ammonia sensing at room temperature

Im,

Lee,

Kim

et al. 2024

Mater. Horiz.

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Introducing Benzene-1,3,5-tri(dithiocarboxylate) as a Multidentate Linker in Coordination Chemistry

Cited by 3 publications

References 51 publications

Metal-Tuned Ligand Reactivity Enables CX₂ (X = O, S) Homocoupling with Spectator Cu Centers

Metal-Tuned Ligand Reactivity Enables CX₂ (X = O, S) Homocoupling with Spectator Cu Centers

Benzene-1,4-Di(dithiocarboxylate) Linker-Based Coordination Polymers of Mn²⁺, Zn²⁺, and Mixed-Valence Fe^2+/3+

Single stranded 1D-helical Cu coordination polymer for ultra-sensitive ammonia sensing at room temperature

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Introducing Benzene-1,3,5-tri(dithiocarboxylate) as a Multidentate Linker in Coordination Chemistry

Cited by 3 publications

References 51 publications

Metal-Tuned Ligand Reactivity Enables CX2 (X = O, S) Homocoupling with Spectator Cu Centers

Metal-Tuned Ligand Reactivity Enables CX2 (X = O, S) Homocoupling with Spectator Cu Centers

Benzene-1,4-Di(dithiocarboxylate) Linker-Based Coordination Polymers of Mn2+, Zn2+, and Mixed-Valence Fe2+/3+

Single stranded 1D-helical Cu coordination polymer for ultra-sensitive ammonia sensing at room temperature

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Product

Resources

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Metal-Tuned Ligand Reactivity Enables CX₂ (X = O, S) Homocoupling with Spectator Cu Centers

Metal-Tuned Ligand Reactivity Enables CX₂ (X = O, S) Homocoupling with Spectator Cu Centers

Benzene-1,4-Di(dithiocarboxylate) Linker-Based Coordination Polymers of Mn²⁺, Zn²⁺, and Mixed-Valence Fe^2+/3+