Reversible Small‐Molecule Interactions with Coordinatively Unsaturated Metal Centers Held in Metallathiaborane Clusters

Bould, Jonathan; Passarelli, Vincenzo; Oro, Luis A.; Macı́as, Ramón

doi:10.1002/ejic.201700539

Cited by 8 publications

(24 citation statements)

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“…Therefore, the CO-ligated system exhibits an opposite behavior compared to that of 2, with the symmetric conformer being the major isomer in solution at all temperatures. The variable-temperature 1 H−{ 11 B} resonances of the cage bridging hydrogen atoms for both compounds also feature similar behavior (Figure S7).…”

Section: ■ Results and Discussionmentioning

confidence: 68%

“…0.12 Å shortening reflects the smaller covalent radius of Ni (1.24 Å) compared to that of Pd (1.39 Å) . The structure differs considerably from that of thiaborane analogue [8,8-(dppe)- nido -8,7-NiSB 9 H 11 ] in which a B–H vertex is subrogated by a sulfur atom and the two bridging B–H–B hydrogen atoms occupy different positions on the pentagonal open face (schematic structures in Scheme ). These structural changes can be rationalized as a consequence of different metal-to-ligand interactions, a point that is discussed in the next section.…”

Section: Resultsmentioning

confidence: 98%

“…Structurally, the compound is analogous to a number of nido-metallundecaborane clusters such as [8,8- 11 The presence of the nickel vertex reduces the metal−B distances in the metallaborane cluster, for example, Ni (7) . 14 The ca.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Structurally, the compound is analogous to a number of nido -metallundecaborane clusters such as [8,8-(PPh 3 ) 2 - nido -8,7-RhSB 9 H 10 ], [μ-2,7-(SCSNEt 2 )(PMe 2 Ph)- nido -PtB 10 H 11 ], [(PMe 2 Ph) 2 - nido -MB 10 H 12 ] (M = Pt, Pd), and the nickelathiaborane analogue [8,8-(dppe)- nido -8,7-NiSB 9 H 11 ] . The presence of the nickel vertex reduces the metal–B distances in the metallaborane cluster, for example, Ni(7) to B(8) and B(11) are 2.207(5) and 2.183(5) Å in 1 compared to 2.324(2) and 2.314(2) Å in [(PMe 2 Ph) 2 - nido -PdB 10 H 12 ] .…”

Section: Resultsmentioning

confidence: 99%

“…11 B and 1 H and Data for [(dppe)NiB 10 H 12 ] (1), [(EtNC)(dppe)NiB 10 H 12 ] (2), [(CO)(dppe)NiB 10 H 12 ] (3), and [(EtNC) 3 NiB 10 H 12 ] (4) at 300 K in CD 2 Cl 2 Solution Together with DFT-GIAO Calculated Boron Shieldings Doublets, with 2 J( 11 B− 1 H)/Hz given in [brackets] for resonances sharp enough to be measurable. b Terminal hydrogen atom resonances obscured by the large excess of EtNC.…”

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confidence: 99%

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Ligand Lability Driven by Metal-to-Borane Pseudorotation: A Mechanism for Ligand Exchange

et al. 2020

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The discovery of systems that interact with small molecules plays a vital facilitating role in the development of devices that show sensitivity to their surroundings and an ability to quickly relay chemical and physical information. Herein, we report on the reaction of [NiCl 2 (dppe)] with decaborane that produces in usable yield a new 11-vertex nickelaborane, [7,7-(dppe)-nido-7-NiB 10 H 12 ] (1), which shows interesting reactivity and functionality toward carbon monoxide and ethylisonitrile. This contribution describes the synthesis and full structural characterization of 1 and its smallmolecule EtNC and CO adducts, 2 and 3, and delineates the dynamic molecular behavior of all of these species in solution. This information sets a foundation from which more advanced work on this and related metallaborane systems can be conceived and provides a more general reference to how NMR spectroscopy, combined with DFT calculations, can be used to analyze the precise locomotion of labile ligands around a metal center held within a borane cluster.

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Section: ■ Results and Discussionmentioning

confidence: 68%

Section: Resultsmentioning

confidence: 98%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

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Ligand Lability Driven by Metal-to-Borane Pseudorotation: A Mechanism for Ligand Exchange

et al. 2020

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White‐Light‐Emitting Materials Constructed from Supramolecular Approaches

Wang

2018

Advanced Optical Materials

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White‐light emissive materials are gaining increasing attentions, ascribed to the potential applications in display and lighting devices as well as sensors. The realization of white‐light emission demands either the simultaneous emission of red, green, and blue colors or at least two complementary colors with similar distribution of emission intensities covering the entire visible spectrum. The introduction of supramolecular approaches not only relieves the negative effects of intermolecular interactions and energy transfer processes, but also endows the white‐light emissive materials with the capacity of color tunability and stimuli‐responsiveness, due to the dynamic and reversible nature of noncovalent interactions. Supramolecular materials with well‐ordered structures can regulate the energy transfer by the assembly–disassembly process, and meanwhile bring in extra fascinating attributes. This review mainly describes the recent reports on fabricating white‐light‐emitting materials from supramolecular approaches such as hydrogen bonding, host–guest interaction, π–π stacking, and metal coordination, which enriches the conceptions and pathways to afford such materials. Moreover, some perspectives together with pressing challenges are presented in the end, synchronously forecasting the potential trends of white‐light emissive materials.

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