Coupling of Allenes with μ‐Alkylidyne Ligands in Diiron Complexes: Synthesis of Novel Bridging Thio‐ and Aminobutadienylidene Complexes

Busetto, Luigi; Marchetti, Fabio; Salmi, Mauro; Zacchini, Stefano; Zanotti, Valerio

doi:10.1002/ejic.200800048

Cited by 17 publications

(14 citation statements)

References 49 publications

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“…101.34 (17) C ( In agreement with the allyl-like coordination in A, Fe(2) [Fe(4) in the second independent molecule] is bonded to all three C(13), C (14), and C (15) A further remark concerns the reversibility of the observed γ-deprotonation. Complexes 4 and 8 upon treatment with HSO 3 CF 3 in CH 2 Cl 2 solution are transformed, almost quantitatively, into parent vinyliminium complexes 2a and 2c.…”

Section: Molecule 1 Molecule 2supporting

confidence: 63%

“…[14] The spectroscopic properties of 3 and 4 are obviously similar to those of 5 and 6. The IR spectrum (in CH 2 Cl 2 solution) of 3 shows two νCO absorptions at 1922 and 1582 cm -1 due to the CO ligand and the acyl group, respectively.…”

Section: Resultsmentioning

confidence: 69%

“…In particular, the coordination of the bridging unsaturated C 4 fragment to the diiron core exhibits high delocalization, which can be explained by using three different representation forms: the bridging allylidene (A), the aminoallenylalkylidene (B), and the 1-amino-1,3-butadienylidene (C; Scheme 7). [14] are reported for comparison.…”

Section: Resultsmentioning

confidence: 99%

“…This observation is consistent with the strictly related transformation of diiron butadienylidene 6 into vinyliminium complexes upon protonation with HSO 3 CF 3 , as recently reported. [14] Investigation on the reactivity toward NaH was extended also to diruthenium complex 2d, which is the ruthenium counterpart of 2a. The aim was to evidence possible effects due to the nature of the metal atom (Ru vs. Fe).…”

Section: Molecule 1 Molecule 2mentioning

confidence: 99%

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γ‐Deprotonation of Bridging Vinyliminium Ligands: New Route to Aminobutadienylidene Diiron and Diruthenium Complexes

et al. 2010

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Section: Molecule 1 Molecule 2supporting

confidence: 63%

Section: Resultsmentioning

confidence: 69%

Section: Resultsmentioning

confidence: 99%

Section: Molecule 1 Molecule 2mentioning

confidence: 99%

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γ‐Deprotonation of Bridging Vinyliminium Ligands: New Route to Aminobutadienylidene Diiron and Diruthenium Complexes

et al. 2010

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“…Complexes 8 react with alkynes via removal of the nitrile ligand in mild conditions (vide infra), but they are generally unreactive towards alkenes and allenes. On the other hand, reactions of 1 with a variety of alkenes and allenes take place in the presence of two co‐reactants, i.e. a base, facilitating the deprotonation of the organic substrate, and Me 3 NO, allowing the CO elimination (Scheme ).…”

Section: Reactivity Of Aminoalkylidyne Complexesmentioning

confidence: 99%

Constructing Organometallic Architectures from Aminoalkylidyne Diiron Complexes

Marchetti

2018

Eur J Inorg Chem

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The chemistry of diiron complexes has seen a recent renaissance, due to the prominent role played by the element iron in the development of sustainable synthetic processes and the cooperative effects provided by two metal centers working in concert, that is a concept amazingly exploited by Nature. Aminoalkylidyne derivatives of [Fe 2 Cp 2 (CO) 4 ] are a convenient scaffold to grow organic fragments; in particular, the facile re-[a] received his PhD degree in Chemistry from the University of Bologna in 2003, then he moved to the University of Pisa in 2006, where he is currently Professor of Inorganic Chemistry. He has co-authored over 150 papers in international journals, dealing with several aspects of the coordination chemistry of transition metal compounds. He was awarded the Nasini Prize by the Italian Chemical Society in 2014, for his contribution to the chemistry of group 5 and 6 metal compounds and to the exploration of unconventional modes of metal mediated C-C bond formation. 3990 Scheme 7. Coupling of isocyanide ligands promoted by acetylide addition to aminoalkylidyne complexes. (a) R = Xyl, R′ = Ph; R = Xyl, R′ = 4-C 6 H 4 Me; R = Me, R′ = Ph. (b) γ-Al 2 O 3 , R′ = SiMe 3 . [51]Eur. 3991Scheme 8. Base-assisted coupling of aminoalkylidyne ligand (R = Me, Xyl or 4-C 6 H 4 OMe) with (a) alkenes (R′ = H, R′′ = CN, CO 2 Me, Ph; R′ = R′′ = CO 2 Et) [53] and (b) allenes (R′ = R′′ = Me; R′ = Me, CO 2 Et, R′′ = H). [54] Scheme 9. Synthesis of vinyliminium complexes via alkyne insertion into Fe-μ-carbyne bond. Inset: possible forms of isomerism. [61][62][63] Eur.

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Antiproliferative and bactericidal activity of diiron and monoiron cyclopentadienyl carbonyl complexes comprising a vinyl‐aminoalkylidene unit

Rocco

Busto

Pérez‐Arnaiz

et al. 2020

Applied Organom Chemis

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A series of diiron complexes with two cyclopentadienyls, two carbonyls, and one bridging vinyl-aminoalkylidene as ligands, [3a-h]CF 3 SO 3 and [4a-d] CF 3 SO 3 , was synthesized in 66-94% yields from diiron μ-aminocarbyne precursors. The subsequent reactions with pyrrolidine led to selective fragmentation to aminoalkylidene-ferracyclopentenone derivatives (5a-h and 6a-c) in 30-84% yields. The compounds were characterized by elemental analysis, Fourier transform infrared and NMR spectroscopy, and by single crystal X-ray diffraction in three cases. The stability in aqueous media relevant to biological trials, the carbon monoxide release, and the catalytic activity in NADH oxidation were evaluated for selected compounds by NMR spectroscopy and gas chromatography. The in vitro antiproliferative activity of the compounds was determined towards cancer (A2780, A2780cisR) and noncancer (HEK-293) cell lines. Moreover, the antibacterial activity was tested on Gram-positive (vancomycin-resistant E. faecium and methicillin-resistant S. aureus) and Gram-negative strains (A. baumannii and P. aeruginosa). K E Y W O R D S amino-alkylidene ligand, bioorganometallic chemistry, cytotoxic and antibacterial activity, diiron complexes, iron-carbonyl complexes Dalila Rocco and Natalia Busto contributed equally to the work.

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Coupling of Allenes with μ‐Alkylidyne Ligands in Diiron Complexes: Synthesis of Novel Bridging Thio‐ and Aminobutadienylidene Complexes

Cited by 17 publications

References 49 publications

γ‐Deprotonation of Bridging Vinyliminium Ligands: New Route to Aminobutadienylidene Diiron and Diruthenium Complexes

γ‐Deprotonation of Bridging Vinyliminium Ligands: New Route to Aminobutadienylidene Diiron and Diruthenium Complexes

Constructing Organometallic Architectures from Aminoalkylidyne Diiron Complexes

Antiproliferative and bactericidal activity of diiron and monoiron cyclopentadienyl carbonyl complexes comprising a vinyl‐aminoalkylidene unit

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