1,2-Diselenolene ligands and related metal complexes: Design, synthesis and applications

Pintus, Anna; Arca, Massimiliano

doi:10.1016/j.ccr.2022.214444

Cited by 3 publications

(2 citation statements)

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“…Interestingly, further treatment of 13a and 13b with S 8 indicated the generation of mixed sulfur–selenium species of the type [Co 2 (BPMP)((CO 2 R) Se CC S (CO 2 R))] 1+ (R = Me, Et) along with 12a / 12b (Figures S91–S98). While the partial or complete substitution of the selenium atoms by sulfur atoms in the coordinated diselenolenes is not unprecedented in the literature, the previous reports include strictly the organometallic complexes of cobalt for such reactions. − Although the exact mechanism for such reactions could not be established, it was proposed , that the integrity of the C–Se bond in the metal–diselenolene complexes might be lost in the presence of elemental sulfur. This situation might lead to the generation of free alkyne and elemental selenium in the reaction solution, which, in the presence of elemental sulfur, might generate the dithiolene or mixed selenolatothiolato species. , …”

Section: Resultsmentioning

confidence: 99%

Generation and Reactivity of Polychalcogenide Chains in Binuclear Cobalt(II) Complexes

Hossain,

Roy Choudhury,

Majumdar

2024

JACS Au

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A series of six binuclear Co(II)−thiolate complexes, [Co 2 (BPMP)(S−C 6 H 4 -o-X) 2 ] 1+ (X = OMe, 2; NH 2 , 3), [Co 2 (BPMP)(μ-S−C 6 H 4 -o-O)] 1+ (4), and [Co 2 (BPMP)(μ-Y)] 1+ (Y = bdt, 5; tdt, 6; mnt, 7), has been synthesized from [Co 2 (BPMP)(MeOH) 2 (Cl) 2 ] 1+ (1a) and [Co 2 (BPMP)(Cl) 2 ] 1+ (1b), where BPMP 1− is the anion of 2,6-bis[[bis(2-pyridylmethyl)amino]methyl]-4-methylphenol. While 2 and 3 could allow the two-electron redox reaction of the two coordinated thiolates with elemental sulfur (S 8 ) to generate [Co 2 (BPMP)(μ-S 5 )] 1+ (8), the complexes, 4−7, could not undergo a similar reaction. An analogous redox reaction of 2 with elemental selenium ([Se]) produced [{Co 2 (BPMP)(μ-Se 4 )}{Co 2 (BPMP)(μ-Se 3 )}] 2+ (9a) and [Co 2 (BPMP)(μ-Se 4 )] 1+ (9b). Further reaction of these polychalcogenido complexes, 8 and 9a/9b, with PPh 3 allowed the isolation of [Co 2 (BPMP)(μ-S)] 1+ (10) and [Co 2 (BPMP)(μ-Se 2 )] 1+ (11), which, in turn, could be converted back to 8 and 9a upon treatment with S 8 and [Se], respectively. Interestingly, while the redox reaction of the polyselenide chains in 9a and 11 with S 8 produced 8 and [Se], the treatment of 8 with [Se] gave back only the starting material (8), thus demonstrating the different redox behavior of sulfur and selenium. Furthermore, the reaction of 8 and 9a/9b with activated alkynes and cyanide (CN − ) allowed the isolation of the complexes, [Co 2 (BPMP)(μ-E 2 C 2 (CO 2 R) 2 )] 1+ (E = S: 12a, R = Me; 12b, R = Et; E = Se: 13a, R = Me; 13b, R = Et) and [Co 2 (BPMP)(μ-SH)(NCS) 2 ] (14), respectively. The present work, thus, provides an interesting synthetic strategy, interconversions, and detailed comparative reactivity of binuclear Co(II)−polychalcogenido complexes.

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Section: Resultsmentioning

confidence: 99%

Generation and Reactivity of Polychalcogenide Chains in Binuclear Cobalt(II) Complexes

Hossain,

Roy Choudhury,

Majumdar

2024

JACS Au

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“…[34] Furthermore, the synthesis of organoselenium compounds has gained recent significant attention, especially due to the fact of their interesting, and somewhat unique properties and applications. [34][35][36][37][38][39][40] We were pleased to find that diphenyldiselenide was successfully silylated/germylated under standard conditions (Scheme 3), leading to products 7 a and 7 b in very good yields (86-88 %).…”

Section: Resultsmentioning

confidence: 99%

Ru‐catalyzed Formation of Thiosilanes and Selenosilanes using Dichalcogenides as a User‐Friendly Alternative to Thiols and Selenols

2022

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A ruthenium-catalyzed reaction for the selective transformation of disulfides (and diselenides) into their silyl (and germyl) counterparts has been developed, as the first example of a thiol/thiolate-free protocol. Our strategy employs commercially available ruthenium dodecacarbonyl as the catalyst in combina-tion with user-friendly hydrosilanes (and hydrogermanes) and odorless dichalcogenides (S, Se). Further derivatization of heteroaryl halides into unsymmetrical sulfides demonstrated the synthetic potential of the obtained silylthioethers.

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Nature and strength of metal-dichalcogenolate bond in homoleptic square-planar d8 metal bis(1,2-dichalcogenolate) complexes [M(E2C2(CN)2)2]2– (E=S, Se, Te; M=Ni(II), Pd(II), Pt(II)): A DFT study

Najafi,

Gholiee

2023

Journal of Organometallic Chemistry

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1,2-Diselenolene ligands and related metal complexes: Design, synthesis and applications

Cited by 3 publications

References 393 publications

Generation and Reactivity of Polychalcogenide Chains in Binuclear Cobalt(II) Complexes

Generation and Reactivity of Polychalcogenide Chains in Binuclear Cobalt(II) Complexes

Ru‐catalyzed Formation of Thiosilanes and Selenosilanes using Dichalcogenides as a User‐Friendly Alternative to Thiols and Selenols

Nature and strength of metal-dichalcogenolate bond in homoleptic square-planar d8 metal bis(1,2-dichalcogenolate) complexes [M(E2C2(CN)2)2]2– (E=S, Se, Te; M=Ni(II), Pd(II), Pt(II)): A DFT study

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