A Comprehensive Analysis of the Metal–Nitrile Bonding in an Organo-Diiron System

Bresciani, Giulio; Biancalana, Lorenzo; Pampaloni, Guido; Zacchini, Stefano; Ciancaleoni, Gianluca; Marchetti, Fabio

doi:10.3390/molecules26237088

Cited by 21 publications

(18 citation statements)

References 88 publications

(92 reference statements)

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“…In fact, previous findings indicated that R may significantly affect the chemistry of this class of complexes [ 37 ]. Compounds [1a–d]CF 3 SO 3 were converted into the respective acetonitrile adducts [ 40 ] using the trimethylamine- N -oxide (TMNO) strategy, which is often reliable with cationic complexes based on the {M 2 Cp 2 (CO) 3 } core with M = Fe or Ru [ 41 , 42 , 43 , 44 ]. The resulting derivatives [1a NCMe –1d NCMe ]CF 3 SO 3 were used in all cases as freshly prepared reactants.…”

Section: Resultsmentioning

confidence: 99%

Diiron Aminocarbyne Complexes with NCE− Ligands (E = O, S, Se)

et al. 2023

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Diiron μ-aminocarbyne complexes [Fe2Cp2(NCMe)(CO)(μ-CO){μ-CN(Me)(R)}]CF3SO3 (R = Xyl, [1aNCMe]CF3SO3; R = Me, [1bNCMe]CF3SO3; R = Cy, [1cNCMe]CF3SO3; R = CH2Ph, [1dNCMe]CF3SO3), freshly prepared from tricarbonyl precursors [1a–d]CF3SO3, reacted with NaOCN (in acetone) and NBu4SCN (in dichloromethane) to give [Fe2Cp2(kN-NCO)(CO)(μ-CO){μ-CN(Me)(R)}] (R = Xyl, 2a; Me, 2b; Cy, 2c) and [Fe2Cp2(kN-NCS)(CO)(μ-CO){μ-CN(Me)(CH2Ph)}], 3 in 67–81% yields via substitution of the acetonitrile ligand. The reaction of [1aNCMe–1cNCMe]CF3SO3 with KSeCN in THF at reflux temperature led to the cyanide complexes [Fe2Cp2(CN)(CO)(μ-CO){μ-CNMe(R)}], 6a–c (45–67%). When the reaction of [1aNCMe]CF3SO3 with KSeCN was performed in acetone at room temperature, subsequent careful chromatography allowed the separation of moderate amounts of [Fe2Cp2(kSe-SeCN)(CO)(μ-CO){μ-CN(Me)(Xyl)}], 4a, and [Fe2Cp2(kN-NCSe)(CO)(μ-CO){μ-CN(Me)(Xyl)}], 5a. All products were fully characterized by elemental analysis, IR, and multinuclear NMR spectroscopy; moreover, the molecular structure of trans-6b was ascertained by single crystal X-ray diffraction. DFT calculations were carried out to shed light on the coordination mode and stability of the {NCSe-} fragment.

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Section: Resultsmentioning

confidence: 99%

Diiron Aminocarbyne Complexes with NCE− Ligands (E = O, S, Se)

et al. 2023

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“…Quantitative PPh 3 /MeCN replacement was achieved by heating a solution of 1 in acetonitrile at reflux, affording complex 2 in 95% yield ( Scheme 1 ). Note that nitrile ligands usually behave as labile ones and are easily replaced by phosphines when coordinated to group 8 41 − 44 or other transition metals. 45 , 46 In the present case, the reversed reaction is probably favored by steric factors arising from two bulky triphenylphosphines occupying adjacent coordination sites in 1 .…”

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confidence: 99%

Ruthenium(II)–Tris-pyrazolylmethane Complexes Inhibit Cancer Cell Growth by Disrupting Mitochondrial Calcium Homeostasis

et al. 2022

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While ruthenium arene complexes have been widely investigated for their medicinal potential, studies on homologous compounds containing a tridentate tris(1-pyrazolyl)methane ligand are almost absent in the literature. Ruthenium(II) complex 1 was obtained by a modified reported procedure; then, the reactions with a series of organic molecules (L) in boiling alcohol afforded novel complexes 2 – 9 in 77–99% yields. Products 2–9 were fully structurally characterized. They are appreciably soluble in water, where they undergo partial chloride/water exchange. The antiproliferative activity was determined using a panel of human cancer cell lines and a noncancerous one, evidencing promising potency of 1 , 7 , and 8 and significant selectivity toward cancer cells. The tested compounds effectively accumulate in cancer cells, and mitochondria represent a significant target of biological action. Most notably, data provide convincing evidence that the mechanism of biological action is mediated by the inhibiting of mitochondrial calcium intake.

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“…The common feature in the synthesis of 2 – 4 is the elimination of one carbon monoxide ligand by means of the trimethylamine‐N‐oxide strategy. [ 48 ] Thus, when the reaction with trimethylamine‐N‐oxide is conducted in acetonitrile, a labile nitrile adduct is formed, [ 49 ] and the subsequent treatment with either NaBH 4 , NBu 4 CN or LiCl results in the formation of neutral products. Within the 2a – c series, [Fe 2 (μ‐H)Cp 2 (CO) 2 {μ‐CN (Me)(Xyl)}], 2c , was previously reported, [ 50 ] whereas [Fe 2 (μ‐H)Cp 2 (CO) 2 {μ‐CN (Me)(R)}] (R = 4‐C 6 H 4 OMe, 2a ; R = Cy, 2b ) are described here for the first time.…”

Section: Resultsmentioning

confidence: 99%

Diiron bis‐cyclopentadienyl complexes as transfer hydrogenation catalysts: The key role of the bridging aminocarbyne ligand

Bresciani

Biancalana

Zacchini

et al. 2022

Applied Organom Chemis

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The catalytic activity of a series of diiron complexes based on the {Fe 2 Cp 2 (CO) x } core (x = 2-3) and containing a bridging aminocarbyne ligand was screened in transfer hydrogenation reaction of cyclohexanone from isopropanol. The series includes cationic tricarbonyl complexes, [1a-d]CF 3 SO 3 , and neutral derivatives obtained by substitution of one carbonyl with hydride (2a-c), cyanide (3a-d) or chloride (4a) ligands. The novel compounds 2a-b, 3a-b and 4a were characterized by analytical and spectroscopic techniques, and the single crystal X-ray structure of one isomer of 4a was determined. In general, diiron complexes exhibited a moderate activity in combination with potassium hydroxide; [Fe 2 Cp 2 (CN)(CO)(μ-CO){μ-CN (Me)(4-C 6 H 4 OMe)}], 3a, emerged as the best catalyst, and the study of its activity was extended to a range of other ketones. DFT calculations suggest an unusual carbyne-centred mechanism, and the better performance displayed by 3a is ascribable to the stabilizing effect provided by the cyanide co-ligand, which is experimentally supported by IR analyses.

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A Comprehensive Analysis of the Metal–Nitrile Bonding in an Organo-Diiron System

Cited by 21 publications

References 88 publications

Diiron Aminocarbyne Complexes with NCE− Ligands (E = O, S, Se)

Diiron Aminocarbyne Complexes with NCE− Ligands (E = O, S, Se)

Ruthenium(II)–Tris-pyrazolylmethane Complexes Inhibit Cancer Cell Growth by Disrupting Mitochondrial Calcium Homeostasis

Diiron bis‐cyclopentadienyl complexes as transfer hydrogenation catalysts: The key role of the bridging aminocarbyne ligand

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