Bridging vinylalkylidene transition metal complexes

Busetto, Luigi; Maitlis, Peter M.; Zanotti, Valerio

doi:10.1016/j.ccr.2009.07.022

Cited by 37 publications

(28 citation statements)

References 119 publications

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“…Conversely, [ 17 – 18 ]CF 3 SO 3 , bearing a C 2 ‐substituent (R′′), are found in the Z conformation, whereby the xylyl group points away from R′′. The most salient NMR features are represented by the resonances of the C 1 and C 3 carbons, found between 218–233 ppm and 171–208 ppm, in agreement with their amino‐alkylidene and alkylidene nature, respectively. The 19 F NMR spectra of [ 2 – 19 ]CF 3 SO 3 (in D 2 O) exhibit the singlet related to the triflate anion at about −79 ppm.…”

Section: Resultsmentioning

confidence: 96%

Anticancer Potential of Diiron Vinyliminium Complexes

Rocco

Batchelor

Agonigi

et al. 2019

Chemistry A European J

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Although ferrocene derivatives have attracted considerable attention as possible anticancer agents, the medicinal potential of diiron complexes has remained largely unexplored. Herein, we describe the straightforward multigram‐scale synthesis and the antiproliferative activity of a series of diiron cyclopentadienyl complexes containing bridging vinyliminium ligands. IC50 values in the low‐to‐mid micromolar range were determined against cisplatin sensitive and resistant human ovarian carcinoma (A2780 and A2780cisR) cell lines. Notable selectivity towards the cancerous cells lines compared to the non‐tumoral human embryonic kidney (HEK‐293) cell line was observed for selected compounds. The activity seems to be multimodal, involving reactive oxygen species (ROS) generation and, in some cases, a fragmentation process to afford monoiron derivatives. The large structural variability, amphiphilic character and good stability in aqueous media of the diiron vinyliminium complexes provide favorable properties compared to other widely studied classes of iron‐based anticancer candidates.

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Section: Resultsmentioning

confidence: 96%

Anticancer Potential of Diiron Vinyliminium Complexes

Rocco

Batchelor

Agonigi

et al. 2019

Chemistry A European J

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“…Formation of a CC bond through CH activation of an olefin is remarkable in consideration of the relatively mild reaction conditions (i.e., NaH is unable to carry out olefin deprotonation by itself), which evidences the role of diiron coordination. On the other hand, the stability of the resulting bridging vinylalkylidene30 also contributes to the observed transformations.…”

Section: Cc Bond Formation At Bridging C1 Ligands In Diiron Complexesmentioning

confidence: 99%

“…The reactivity of these bridging C 3 fragment consequently accounts for a rather complex amount of observations that are difficult to summarise, even though restricted to diiron complexes. Specific review articles on allenes,92 allenyls and propargyls93 and vinylalkylidenes30 have been published, providing information that also include diiron complexes. This chapter will offer a few selected examples, mostly concerning bridging allenyl and vinyliminium ligands, aimed at remarking the huge potential represented by bridging C 3 ligands in bond‐forming reactions, which so far has been underexploited for possible synthetic applications.…”

Section: Cc Bond Formation At Bridging C3 Ligands In Diiron Complexesmentioning

confidence: 99%

CC Bond Formation in Diiron Complexes

Mazzoni

Salmi

Zanotti

2012

Chemistry A European J

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The growing effort to design new sustainable synthetic methodologies, based on readily available and environmentally friendly transition metals, has boosted research on iron complexes. This review article focuses on C-C-bond-forming reactions occurring at bridging ligands in diiron complexes, aimed at evidencing distinctive aspects and advantages associated with the presence of two adjacent iron centres. A number of diiron-mediated C-C-bond-forming reactions reported in the literature, including nucleophilic and electrophilic additions and insertion and cycloaddition reactions, have been accumulated over the years, which, together with more recent developments, indicate that diiron complexes might provide promising alternatives to precious metals in the challenging field of metal-promoted C-C bond formation.

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“…As an example, µ-dithiolate diiron has been very actively investigated as mimics of [FeFe]-H 2 ases active site and as potential catalysts for hydrogen evolution [26][27][28][29]. The second peculiar feature of diiron complexes is the possibility of observing bridging coordination of a variety of carbon-based ligands (including isocyanides and hydrocarbyl ligands derived from CNR ligands), which potentially provide access to activation modes and reaction profiles not observed when the same ligands are bound to a single metal atom [30][31][32].…”

Section: Introductionmentioning

confidence: 99%

Bond Forming Reactions Involving Isocyanides at Diiron Complexes

et al. 2019

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The versatility of isocyanides (CNR) in organic chemistry has been tremendously enhanced by continuous advancement in transition metal catalysis. On the other hand, the urgent need for new and more sustainable synthetic strategies based on abundant and environmental-friendly metals are shifting the focus towards iron-assisted or iron-catalyzed reactions. Diiron complexes, taking advantage of peculiar activation modes and reaction profiles associated with multisite coordination, have the potential to compensate the lower activity of Fe compared to other transition metals, in order to activate CNR ligands. A number of reactions reported in the literature shows that diiron organometallic complexes can effectively assist and promote most of the “classic” isocyanide transformations, including CNR conversion into carbyne and carbene ligands, CNR insertion, and coupling reactions with other active molecular fragments in a cascade sequence. The aim is to evidence the potential offered by diiron coordination of isocyanides for the development of new and more sustainable synthetic strategies for the construction of complex molecular architectures.

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Bridging vinylalkylidene transition metal complexes

Cited by 37 publications

References 119 publications

Anticancer Potential of Diiron Vinyliminium Complexes

Anticancer Potential of Diiron Vinyliminium Complexes

CC Bond Formation in Diiron Complexes

Bond Forming Reactions Involving Isocyanides at Diiron Complexes

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