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40 pages, 25175 KB

Open AccessReview

1,1′-Disubstituted Ferrocene Ligand Scaffolds Featuring Pnictogens Other than Phosphorus as Donor Sites

by Subhayan Dey and Rudolf Pietschnig

Molecules 2024, 29(22), 5283; https://doi.org/10.3390/molecules29225283 - 8 Nov 2024

Cited by 5 | Viewed by 4678

The chemistry of bidentate ligands with a dppf-like motif, where phosphorus is fully or partially replaced by other pnictogens as donor sites, is summarized and discussed in this comprehensive review, while covering the literature from 1966 to 2024, related to more than 165 original references and discussing more than 75 independent chemical entities (1–41). Besides addressing synthetic, structural, and electrochemical aspects of such compounds, their donor properties and metal coordination behavior is discussed, along with catalytic applications. Based on their electronic and steric situations, trends in the performance of such compounds, either as ligands for catalysis or on their own merits for non-catalytic purposes, have been elucidated. Related topics that could not be covered in this article have been acknowledged by referring to the literature for completeness. Full article

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10 pages, 7661 KB

Open AccessArticle

Coordination of a Pyrazole Functionalized Acetylacetone to the Coinage Metal Cations: An Unexpected Packing Similarity and a Trinuclear Cu^II/Au^I Complex

by Steven van Terwingen, Ben Ebel, Noah Nachtigall and Ulli Englert

Crystals 2022, 12(7), 984; https://doi.org/10.3390/cryst12070984 - 15 Jul 2022

Cited by 1 | Viewed by 2318

Abstract

The heteroditopic molecule HacacMePz combines a Pearson hard acetylacetone donor site with a softer trimethylpyrazole and shows site selectivity towards the coinage metal cations. The coordination of the N donor function was achieved towards Ag^I and Au^I, leading to the salt [Ag(HacacMePz)₂]PF₆ (1) and the neutral complex [AuCl(HacacMePz)] (2). In either case, linear coordination about the coinage metal cation is observed. Interestingly, both complexes crystallize in space group

P b c a

with similar cell parameters. The two solids do not qualify as isostructural, albeit being closely related in real and reciprocal space. To probe the ligand’s ability for the envisaged synthesis of bimetallic coordination polymers, the mixed-metal Cu^II/Au^I complex [Cu(acacMePzAuCl)₂] (3) was obtained. In this mixed-metal oligomer, the central Cu^II cation adopts a square planar coordination environment with two O,O^′-coordinated acacMePz⁻ ligands, whose softer N donor sites are saturated with a AuCl moiety. Full article

(This article belongs to the Special Issue Mixed-Metal Coordination Polymers)

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18 pages, 4108 KB

Open AccessArticle

Possible Synthetic Approaches for Heterobimetallic Complexes by Using nNHC/tzNHC Heteroditopic Carbene Ligands

by Andrea Longhi, Marco Baron, Marzio Rancan, Gregorio Bottaro, Lidia Armelao, Paolo Sgarbossa and Cristina Tubaro

Molecules 2019, 24(12), 2305; https://doi.org/10.3390/molecules24122305 - 21 Jun 2019

Cited by 13 | Viewed by 4404

Abstract

The synthesis of heterobimetallic complexes remains a synthetic challenge in the field of organometallic chemistry. A possible approach in this regard might be the use of a bidentate heteroditopic bis(carbene) ligand that combines an imidazol-2-ylidene (nNHC) with a 1,2,3-triazol-5-ylidene (tzNHC) connected by an organic spacer. The optimized strategy to heterobimetallic complexes with this type of ligand involves a 3-step procedure: (i) Coordination of the nNHC, functionalized with a 1,2,3-triazole ring, to a metal center; (ii) formation of the triazolium ring by alkylation of the triazole N-3; (iii) deprotonation of the tzNHC precursor and coordination of the second metal center. Following this procedure, a novel Au(I)-Ag(I) dinuclear complex was isolated and its properties were compared to the analogous homobimetallic Ag(I)-Ag(I) and Au(I)-Au(I) complexes. The study was completed by the determination of the molecular structures of some synthetic intermediates. Full article

(This article belongs to the Special Issue Mesoionic Carbenes: Exceptionally Electron-Rich Carbon-Donor Ligands in Synthesis, Catalysis, and Materials Science)

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