Supercarboranes: Achievements and perspectives

Jian, Zhang; Xie, Zuowei

doi:10.1351/pac-con-12-07-03

Cited by 18 publications

(4 citation statements)

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“…It is envisaged that a new class of boron clusters of extraordinary size will be prepared as research in this area proceeds. The search for applications of supercarboranes in many disciplines such as BNCT, electronics, catalysis, polymers, and nanomaterials is anticipated in the future …”

Section: Conclusion and Summarymentioning

confidence: 99%

“…This finding offered a critical entry point into the synthesis of supercarboranes . Since then, significant progress has been made in this research area. , This Account summarizes these recent developments in the synthesis, structure, and reactivity of 13- and 14-vertex carboranes. Their numbering systems and color codes are illustrated in Chart .…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Structure, and Reactivity of 13- and 14-Vertex Carboranes

Zhang

Xie

2014

Acc. Chem. Res.

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Carboranes are a class of polyhedral boron hydride clusters in which one or more of the BH vertices are replaced by CH units. Their chemistry has been dominated by 12-vertex carboranes for over half a century. In contrast, knowledge regarding supercarboranes (carboranes with more than 12 vertices) had been limited merely to possible cage geometries predicted by theoretical work before 2003. Only in recent years has significant progress been made in synthesizing supercarboranes. Such a breakthrough relied on the use of Carbon-Atoms-Adjacent (CAd) nido-carborane dianions or arachno-carborane tetraanions as starting materials. In this Account, we describe our work on constructing and elucidating the chemistry of supercarboranes. Earlier attempted insertions of the formal [BR](2+) unit into Carbon-Atoms-Apart (CAp) 12-vertex nido-[7,9-C2B10H12](2-) did not produce the desired 13-vertex carboranes. Such failure is often attributed to the extraordinary stability of the B12 icosahedron (the "icosahedral barrier"). However, the difference in reducing power between CAp and CAd 12-vertex nido-carborane dianions had been overlooked. Our results have shown that CAd nido-carborane dianions are weaker reducing agents than the CAp isomers, allowing a capitation to prevail over a redox reactivity. This finding provides an entry point to the synthesis of supercarboranes and a series of 13- and 14-vertex closo-carboranes have been prepared and structurally characterized. They share some chemical properties with those of 12-vertex carboranes; on the other hand, they have their own unique characteristics. For example, a 13- vertex closo-carborane can undergo single electron reduction to give a stable carborane radical anion with [2n + 3] framework electrons, which can accept one additional electron to form a 13-vertex CAd nido-carborane dianion. 13-Vertex closo-carborane can also react with various nucleophiles to afford the cage carbon and/or boron extrusion products closo-CB11(-), nido-CB10(-), closo-CB10(-), and closo-C2B10, depending on the nature of the nucleophiles. Studies of supercarboranes remain a relative young research area, particularly in comparison to the rich literature of icosahedral carboranes with 12-vertices. Other supercarboranes are expected to be prepared and structurally characterized as the field progresses, and the results detailed here will further these efforts.

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Section: Conclusion and Summarymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, and Reactivity of 13- and 14-Vertex Carboranes

Zhang

Xie

2014

Acc. Chem. Res.

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“…In addition, heteroboranes can accommodate in their structures metal elements from almost all of the periodic table, leading to the synthesis of a huge number of metallaheteroboranes, in which, many times, the heteroborane fragment can be regarded as a subrogate of well-known organic ligands. [5][6][7][8][9][10][11][12][13][14] Bearing in mind that tunable ligands for transition metals constitute a broad field that centers on the idea that one can engender novel reactivity, the flexibility of heteroboranes as face-bound ligands affords interesting possibilities for the design of new systems with potential in the activation of unreactive bonds and ultimately in catalysis. 2,15 In addition, heteroboranes can act as substituents changing the steric and/ or electronic properties of classical ligands.…”

Section: Introductionmentioning

confidence: 99%

Unusual cationic rhodathiaboranes: synthesis and characterization of [8,8,8-(H)(PR₃)₂-9-(Py)-nido-8,7-RhSB₉H₁₀]⁺and [1,3-μ-(H)-1,1-(PR₃)₂-3-(Py)-isonido-1,2-RhSB₉H₈]⁺

et al. 2014

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The treatment of the hydridorhodathiaboranes, [8,8,8-(H)(PR3)2-9-(Py)-nido-8,7-RhSB9H9], where PR3 = PPh3 (2), PMePh2 (3), PPh3 and PMe2Ph (4), or PMe3 and PPh3 (5), and [8,8,8-(H)(PMePh2)2-9-(PMePh2)-nido-8,7-RhSB9H9] (6), with TfOH affords [8,8,8-(H)(PR3)2-9-(Py)-nido-8,7-RhSB9H10](+) cations, where PR3 = PPh3 (12), PMePh2 (13), PPh3 and PMe2Ph (14), or PMe3 and PPh3 (15), and [8,8,8-(H)(PMePh2)2-9-(PMePh2)-nido-8,7-RhSB9H10](+) (16). Compounds 13 and 14 lose H2 to give [1,3-μ-(H)-1,1-(PR3)2-3-(Py)-isonido-1,2-RhSB9H8](+), where PR3 = PMe2Ph (18), PPh3 and PMe2Ph (21), or PMePh2 (22). Similarly, the 11-vertex rhodathiaboranes, [1,1-(PR3)2-3-(Py)-1,2-RhSB9H8], where PR3 = PPh3 (7), PMe2Ph (8), PMe3 (9), or PPh3 and PMe3 (10), react with TfOH to give the corresponding cations, [1,3-μ-(H)-1,1-(PR3)2-3-(Py)-isonido-1,2-RhSB9H8](+), where PR3 = PPh3 (17), PMe2Ph (18), PMe3 (19), or PPh3 and PMe3 (20). Four conformers of 20 are studied by X-ray diffraction methods and DFT-calculations, identifying packing motifs that stabilize different metal-thiaborane linkages, and energy variations that are involved in these conformational changes. It is demonstrated that the proton induces nonrigidity on these clusters as well as an enhancement of their Lewis acidity.

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“…Rational construction and structure–property relationship are always the research targets for coordination polymers (CPs), porous coordination polymers (PCPs), or metal–organic frameworks (MOFs). , In the past two decades, many crystal-engineering methods and classical CPs and PCPs have been developed. Although carboxylate groups have hardly predictable coordination modes, the square-planar Cu 2 (RCOO) 4 , octahedral Zn 4 (μ 4 -O)(RCOO) 6 , trigonal-prismatic M 3 (μ 3 -O)(RCOO) 6 , and cuboctahedral Zr 6 (μ 3 -O) 4 (μ 3 -OH) 4 (RCOO) 12 clusters can be linked by polycarboxylate ligands with different geometries, lengths, and side groups to form PCPs with designable topologies, pore sizes, and pore surface characteristics. − Some of these metal carboxylate frameworks are highly stable because of the strong coordination bonds formed between the high-valence (trivalent and tetravalent) metal ions and carboxylate oxygen atoms. , PCPs can be also rationally constructed by combining anisotropic clusters such as distorted octahedral M 2 (RCOO) 4 (Rpy) 2 and tricapped trigonal prismatic M 3 (μ 3 -O)(RCOO) 6 (Rpy) 3 clusters with mixed polycarboxylate/pyridyl ligands. , For pure polypyridyl ligands, the simple and predictable coordination mode of the pyridyl ring is ideal for construction of CPs and PCPs, but the metal to ligand ratio is not easy to control and the counteranions usually occupy too much volume of the crystal. Metal pyridyl frameworks are usually much less stable than metal carboxylate frameworks. , …”

Section: Introductionmentioning

confidence: 99%

Cu(I) 3,5-Diethyl-1,2,4-Triazolate (MAF-2): From Crystal Engineering to Multifunctional Materials

Liu

Zhang

Chen

2017

Crystal Growth & Design

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Among various types of nonporous and porous coordination polymers, and as a subset of metal azolate frameworks (MAFs), Cu(I) 1,2,4triazolates are unique for their simple three-connected network topologies which can be controlled by their significant steric hindrance effects between the noncoordinative side groups. This perspective article discusses the crystal engineering, structures, and diversified properties of Cu(I) 1,2,4-triazolates, particularly focusing on the porous coordination polymer [Cu(detz)] (MAF-2, Hdetz = 3,5-diethyl-1,2,4-triazole) showing unique/multimode flexibility, high hydrophobicity, bright phosphorescence, and exceptionally high stabilities toward not only guest change but also water and oxygen, which have demonstrated as a good platform for realizing high-performance applications related to gas/vapor confinement, storage, separation, and sensing. The exceptional O 2 reactivity and the tunable framework flexibility, pore surface polarity, and gas separation performances of [Cu 4 (btm) 2 ] (MAF-42, H 2 btm = bis(5-methyl-1,2,4-triazol-3-yl)methane) are also summarized.

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Supercarboranes: Achievements and perspectives

Cited by 18 publications

References 61 publications

Synthesis, Structure, and Reactivity of 13- and 14-Vertex Carboranes

Synthesis, Structure, and Reactivity of 13- and 14-Vertex Carboranes

Unusual cationic rhodathiaboranes: synthesis and characterization of [8,8,8-(H)(PR₃)₂-9-(Py)-nido-8,7-RhSB₉H₁₀]⁺and [1,3-μ-(H)-1,1-(PR₃)₂-3-(Py)-isonido-1,2-RhSB₉H₈]⁺

Cu(I) 3,5-Diethyl-1,2,4-Triazolate (MAF-2): From Crystal Engineering to Multifunctional Materials

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Supercarboranes: Achievements and perspectives

Cited by 18 publications

References 61 publications

Synthesis, Structure, and Reactivity of 13- and 14-Vertex Carboranes

Synthesis, Structure, and Reactivity of 13- and 14-Vertex Carboranes

Unusual cationic rhodathiaboranes: synthesis and characterization of [8,8,8-(H)(PR3)2-9-(Py)-nido-8,7-RhSB9H10]+and [1,3-μ-(H)-1,1-(PR3)2-3-(Py)-isonido-1,2-RhSB9H8]+

Cu(I) 3,5-Diethyl-1,2,4-Triazolate (MAF-2): From Crystal Engineering to Multifunctional Materials

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Product

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Unusual cationic rhodathiaboranes: synthesis and characterization of [8,8,8-(H)(PR₃)₂-9-(Py)-nido-8,7-RhSB₉H₁₀]⁺and [1,3-μ-(H)-1,1-(PR₃)₂-3-(Py)-isonido-1,2-RhSB₉H₈]⁺