Synthesis and cluster structure distortions of biscarborane dithiol, thioether, and disulfide

Riffle, Jared R.; Hemingway, Tyler M.; Smith, Mark D.; Peryshkov, Dmitry V.

doi:10.1039/d3dt04289h

Dalton Trans.

2024

DOI: 10.1039/d3dt04289h

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Synthesis and cluster structure distortions of biscarborane dithiol, thioether, and disulfide

Jared R. Riffle,

Tyler M. Hemingway,

Mark D. Smith

et al.

Abstract: The synthesis and structural characterization of the first sulfur-containing derivatives of C,C-biscarborane {ortho-C2B10}2 cluster – thiol, thioether, and disulfide- is reported. The biscarboranyl dithiol (1-HS-C2B10H10)2 exhibits the exceedingly long intracluster...

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Cited by 3 publications

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The First Discovery of Spherical Carborane Molecular Ferroelectric Crystals

Guo,

Yang,

Shu

et al. 2024

Angewandte Chemie

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Carborane compounds, known for their exceptional thermal stability and non‐toxic attributes, have garnered widespread utility in medicine, supramolecular design, coordination/organometallic chemistry, and others. Although there is considerable interest among chemists, the integration of suitable carborane molecules into ferroelectric materials remains a formidable challenge. In this study, we employ the quasi‐spherical design strategy to introduce functional groups at the boron vertices of the o‐carborane cage, aiming to reduce molecular symmetry. This approach led to the successful synthesis of the pioneering ferroelectric crystals composed of cage‐like carboranes: 9‐OH‐o‐carborane (1) and 9‐SH‐o‐carborane (2), which undergo above‐room ferroelectric phase transitions (Tc) at approximately 367 K and 347 K. Interestingly, 1 and 2 represent uniaxial and multiaxial ferroelectrics respectively, with 2 exhibiting six polar axes and as many as twelve equivalent polarization directions. As the pioneering instance of carborane ferroelectric crystals, this study introduces a novel structural archetype for molecular ferroelectrics, thereby providing fresh insights into the exploration of molecular ferroelectric crystals with promising applications.

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The First Discovery of Spherical Carborane Molecular Ferroelectric Crystals

Guo,

Yang,

Shu

et al. 2024

Angewandte Chemie

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The First Discovery of Spherical Carborane Molecular Ferroelectric Crystals

Guo,

Yang,

Shu

et al. 2024

Angew Chem Int Ed

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N–H Bond Activation of Ammonia by a Redox-Active Carboranyl Diphosphine

Humphries,

Tellier,

Smith

et al. 2024

J. Am. Chem. Soc.

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In this work, we report the room-temperature N−H bond activation of ammonia by the carboranyl diphosphine 1-P t Bu 2 -2-P i Pr 2 -closo-C 2 B 10 H 10 (1) resulting in the formation of zwitterionic 7-P(NH 2 ) t Bu 2 -10-P(H) i Pr 2 -nido-C 2 B 10 H 10 (2). Unlike the other phosphorus-based ambiphiles that require geometric constraints to enhance electrophilicity, the new mode of bond activation in this main-group system is based on the cooperation between electron-rich trigonal phosphine centers and the electronaccepting carborane cluster. As an exception among many other metal-based and metal-free systems, the N−H bond activation of gaseous ammonia or aqueous ammonium hydroxide by carboranyl diphosphine 1 proceeds with tolerance of air and water. Mechanistic details of ammonia activation were explored computationally by DFT methods, demonstrating an electrophilic activation of ammonia by the phosphine center. This process is driven by the reduction of the boron cluster followed by an ammonia-assisted deprotonation and proton transfer. A subsequent reaction of 2 and TEMPO results in the cleavage of all N−H and P−H bonds with the formation of a cyclic phosphazenium cation supported by an anionic cluster N(7-P t Bu 2 -8-P i Pr 2 )-nido-C 2 B 9 H 10 (3). Transformations reported herein represent the first example of ammonia oxidation via triple hydrogen atom abstraction facilitated by a metal-free system.

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Synthesis and cluster structure distortions of biscarborane dithiol, thioether, and disulfide

Abstract: The synthesis and structural characterization of the first sulfur-containing derivatives of C,C-biscarborane {ortho-C2B10}2 cluster – thiol, thioether, and disulfide- is reported. The biscarboranyl dithiol (1-HS-C2B10H10)2 exhibits the exceedingly long intracluster...

Cited by 3 publications

References 77 publications

The First Discovery of Spherical Carborane Molecular Ferroelectric Crystals

The First Discovery of Spherical Carborane Molecular Ferroelectric Crystals

The First Discovery of Spherical Carborane Molecular Ferroelectric Crystals

N–H Bond Activation of Ammonia by a Redox-Active Carboranyl Diphosphine

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