Carba-closo-dodecaborate Anions with Two Functional Groups: [1-R-12-HC≡C-closo-1-CB11H10]−(R = CN, NC, CO2H, C(O)NH2, NHC(O)H)

Hailmann, Michael; Konieczka, Szymon Z.; Himmelspach, Alexander; Löblein, Jochen; Reiß, Guido J.; Finze, Maik

doi:10.1021/ic501526g

Cited by 17 publications

(6 citation statements)

References 136 publications

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“…The inner salts H 3 and 4 are oxidized at a higher potential compared to the parent anions 2 and 3 and at a lower potential than 5 . Therefore, a certain degree of transmission of electronic effects through the { closo ‐1‐CB 11 } cage is evident, which is in good agreement to previous studies 11a,11b,29. Since the ferrocenylalkynyl derivatives 1 – 6 as well as H 3 are easier to oxidize than parent ethynylferrocene the boron cages act as electron donors in these compounds.…”

Section: Discussionsupporting

confidence: 91%

“…Thus, the strong σ‐acceptor substituent Me 3 N + bonded to the C cluster atom of 4 shifts the bond properties of the alkynyl moiety towards those of 5 . A related effect was found for the 13 C NMR chemical shifts and hence for the polarization of the electron density of the C≡C triple bond in the respective ethynyl derivatives [12‐HC≡C‐ closo ‐1‐CB 11 H 11 ] – , 1‐Me 3 N‐12‐HC≡C‐ closo ‐1‐CB 11 H 10 , and 9‐HC≡C‐ closo ‐1, 2‐C 2 B 10 H 11 11a,11b. The bond lengths of the [5‐FcC≡C‐ closo ‐1‐C 2 B 9 H 11 ] – ( 6 ) anion are similar to those of 2 and 3 .…”

Section: Resultsmentioning

confidence: 79%

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Boron Clusters with a Ferrocenylalkynyl Group Bonded to Boron: Synthesis, Characterization, and Electrochemical Trends

Schäfer

Krummenacher

Braunschweig

et al. 2015

Zeitschrift anorg allge chemie

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The 12-vertex closo-boron clusters [1-FcCϵC-closo-B 12 H 11 ] 2-(1), [12-FcCϵC-closo-1-CB 11 H 11 ] -(2), [1-H 2 N-12-FcCϵCcloso-1-CB 11 H 10 ] -(3), and [9-FcCϵC-closo-1,2-C 2 B 10 H 11 ] (5) were synthesized from the corresponding iodinated derivatives and Me 3 SiCϵCMgBr by a Pd-catalyzed Kumada-type cross-coupling reaction. Anion 3 was converted into the inner salt [1-Me 3 N-12-FcCϵCcloso-1-CB 11 H 10 ] (4). The nido-derivative [5-FcCϵC-nido-7,8-C 2 B 9 H 11 ] -(6) was obtained from 5 via a deboronation reaction. The * Prof. Dr. M. Finze ARTICLE Scheme 1. {closo-B 12 } (1), {closo-1-CB 11 } (2-4), {closo-1,2-C 2 B 10 } (5), and {nido-7,8-C 2 B 9 } clusters (6) with one ferrocenylalkynyl group bonded to boron.

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Section: Discussionsupporting

confidence: 91%

Section: Resultsmentioning

confidence: 79%

Boron Clusters with a Ferrocenylalkynyl Group Bonded to Boron: Synthesis, Characterization, and Electrochemical Trends

Schäfer

Krummenacher

Braunschweig

et al. 2015

Zeitschrift anorg allge chemie

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“…Thus, all known forms of boron are manmade and exhibit a variety of atomic arrangements, composed of B 12 icosahedra. Following the seminal work of Boustani in 1994, on the geometries of small B clusters, many studies − of their structural evolution have been carried out, both theoretically and experimentally. The mass spectra of B cluster ions reveal high stability of 5, 7, 8, 10, and 11 atom clusters; however, the one case, containing 13 atoms, has anomalously high intensity.…”

Section: Unique Properties Of Clustersmentioning

confidence: 99%

Super Atomic Clusters: Design Rules and Potential for Building Blocks of Materials

2018

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Atomic clusters, consisting of a few to a few thousand atoms, have emerged over the past 40 years as the ultimate nanoparticles, whose structure and properties can be controlled one atom at a time. One of the early motivations in studying clusters was to understand how the properties of matter evolve as a function of size, shape, and composition. Over the past few decades, more than 200 000 papers have been published in this field. These studies have not only led to a considerable understanding of this evolution from clusters to crystals, but also have revealed many unusual size-specific properties that make cluster science an interdisciplinary field on its own, bridging physics, chemistry, materials science, biology, and medicine. More importantly, the possibility of creating a new class of materials, composed of clusters instead of atoms as building blocks, has fueled the hope that one can synthesize materials from the bottom-up with unique and tailored properties. This Review focuses on the properties that set clusters apart from their corresponding bulk. Furthermore, this Review describes how different electron-counting rules can lead to the design of stable clusters, mimicking the chemistry of atoms. We highlight the potential of these "superatoms" as building blocks of cluster-assembled materials. Specifically, we emphasize cluster-inspired materials for energy applications. The concluding section includes a summary of the salient features of clusters, potential challenges that remain, and an outlook for the future of cluster science.

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“…11. 66–74 The reaction conditions used for cross-coupling with anionic polyhedral boranes closely resemble those reported for the neutral carborane cross-coupling, although the poor solubility of the anionic polyhedral boranes in organic solvents such as Et 2 O and toluene can lead to slower catalystic reactivity.…”

Section: Metal-catalyzed B-c Bond Formationmentioning

confidence: 70%

Metal-catalyzed cross-coupling chemistry with polyhedral boranes

2019

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Over the past several decades, metal-catalyzed cross-coupling has emerged as a very powerful strategy to functionalize carbon-based molecules. More recently, some of the cross-coupling methodologies have been adapted to inorganic compounds including boron-rich clusters. The development of this chemistry relies on the ability to synthesize halogenated boron-rich clusters which can serve as electrophilic cross-coupling partners with nucleophilic substrates in the presence of a metal catalyst. While the cross-coupling chemistry with boron-clusters is conceptually reminiscent to that of its hydrocarbon counterparts, several key aspects including the spheroidal bulk of clusters, and the distinct nature of boron-halogen / boron-heteroatom bonds make this chemistry unique. The utility of metal-catalyzed cross-coupling can be extended to several classes of polyhedral boranes including neutral and anionic carboranes, metallaboranes, and carbon-free boranes. Importantly, cross-coupling enables a suite of boron-heteroatom (C, N, O, P, S) couplings to prepare boron cluster-based systems that can be used for ligand design, medicinal chemistry, and materials applications.

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Carba-closo-dodecaborate Anions with Two Functional Groups: [1-R-12-HC≡C-closo-1-CB₁₁H₁₀]⁻(R = CN, NC, CO₂H, C(O)NH₂, NHC(O)H)

Cited by 17 publications

References 136 publications

Boron Clusters with a Ferrocenylalkynyl Group Bonded to Boron: Synthesis, Characterization, and Electrochemical Trends

Boron Clusters with a Ferrocenylalkynyl Group Bonded to Boron: Synthesis, Characterization, and Electrochemical Trends

Super Atomic Clusters: Design Rules and Potential for Building Blocks of Materials

Metal-catalyzed cross-coupling chemistry with polyhedral boranes

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