Chemistry of the boron subhalides. Preparation, boron nuclear magnetic resonance, and thermal stability of tetraboron tetrachloride

Davan, T.; Morrison, John A.

doi:10.1021/ic50201a049

Cited by 26 publications

(5 citation statements)

References 45 publications

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“…Fortunately, unlike (SiO) 4 and (BF) 4 , (BCl) 4 is a known molecule . Consistent with our qualitative arguments and with the computational results in Table , (BCl) 4 is known to have a tetrahedral geometry. , …”

Section: Resultssupporting

confidence: 86%

Why Is (SiO)₄ Calculated To Be Tetrahedral, Whereas (CO)₄ Is Square Planar? A Molecular Orbital Analysis

2013

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Qualitative molecular orbital (MO) theory predicts that square-planar tetrasilacyclobutanetetraone D4h-(SiO)4 should, like D4h-(CO)4, have a triplet ground state, and the results of the (U)CCSD(T)-F12b/cc-pVTZ-F12//(U)B3LYP/6-311+G(2df) calculations, reported here, confirm this expectation. Calculations at the same level of theory find that square-planar tetrasilacyclobutanetetrathione D4h-(SiS)4 also has a triplet ground state. However, these ab initio calculations predict that (SiO)4 and (SiS)4 both have a singlet state of much lower energy, with a tetrahedral (Td) equilibrium geometry and six, electron-deficient, Si-Si bonds. In contrast, the lowest singlet state of (CO)4 and of (CS)4 is calculated to prefer a D4h to a Td geometry. An analysis, based on the second-order Jahn-Teller effect, rationalizes the influence of the electronegativity difference between A and Y in (AY)4 on the energy difference between a D4h and Td geometry. This analysis predicts that (BF)4 and (BCl)4, which are isoelectronic with, respectively, (CO)4 and (CS)4, should both prefer a Td to a D4h equilibrium geometry. These qualitative predictions have been confirmed by our calculations, and (BCl)4 is known experimentally to have a Td equilibrium geometry.

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Section: Resultssupporting

confidence: 86%

Why Is (SiO)₄ Calculated To Be Tetrahedral, Whereas (CO)₄ Is Square Planar? A Molecular Orbital Analysis

2013

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“…The smallest boron-based clusters known are the deltahedral tetraboranes. , In contrast to higher-membered congeners (e.g., B 6 or B 12 ), these clusters do not display the expected 2 n + 2 bonding electron count that is commonly encountered in 3D aromatic boron clusters. , The first known boron tetrahedrane, tetraboron tetrachloride, was reported in 1952 as a thermal decomposition product of B 2 Cl 4 (Figure ), obtained only in small yields, and its solid-state X-ray structure was subsequently solved in 1953 . The early procedures for synthesizing this molecule involved either electrical or microwave discharges in the presence of BCl 3 and mercury, with more recent procedures that produce workable yields involving the reduction of R–BF 2 fragments by a sodium/potassium alloy in alkane solvents. , Alternatively, B 4 R n Cl 4– n ( n = 1, 2, 4) analogues have been synthesized through treatment of the halogenated B 4 Cl 4 cluster with alkyllithium reagents. , The reactivity of B 4 Cl 4 has been described by Morrison and is summarized in Figure …”

Section: Synthesis Of Perfunctionalized Boron Clustersmentioning

confidence: 99%

Synthesis and Applications of Perfunctionalized Boron Clusters

et al. 2018

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This Viewpoint Article describes major advances pertaining to perfunctionalized boron clusters in synthesis and their respective applications. The first portion of this work highlights key synthetic methods allowing one to access a wide range of polyhedral boranes (B4 and B6 – B12 cluster cores) that contain exhaustively functionalized vertices. The second portion of this Viewpoint showcases the historical developments in using these molecules for applications ranging from materials science to medicine. Lastly, we suggest potential new directions for these clusters as they apply to both synthetic methods and applications.

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“…In diesem Sinne schlugen Kleier und Mitarbeiter auf der Basis quantenchemischer Rechnungen 1980 einen Tetrahedran‐Cyclotetraboran‐Tetrahedran‐Isomerisierungsprozess vor 7. 1979 berichteten Morrison und Mitarbeiter über eine ähnliche Herstellung einer Mischung von B 2 Cl 4 und B 4 Cl 4 aus BCl 3 unter Verwendung von Radiofrequenz‐Entladungen 8…”

Section: Introductionunclassified

Dehydrogenation of Perfluoroalkyl Ketones by Using a Recyclable Oxoammonium Salt

2013

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A novel dehydrogenation reaction of perfluoroalkyl ketones by the oxoammonium salt 4‐acetylamino‐2,2,6,6‐tetramethylpiperidine‐1‐oxoammonium tetrafluoroborate (4‐NHAc‐TEMPO+BF4–, Bobbitt's salt, 1) is described. The reaction proceeds under mildly basic conditions and appears to be unique to perfluoroalkyl ketones. A proposed mechanism for this unusual transformation is given. The byproduct of the reaction, 4‐acetylamino‐2,2,6,6‐tetramethyl‐1‐piperidinyloxy (1a), can easily be recovered and used to regenerate the oxoammonium salt.

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Chemistry of the boron subhalides. Preparation, boron nuclear magnetic resonance, and thermal stability of tetraboron tetrachloride

Cited by 26 publications

References 45 publications

Why Is (SiO)₄ Calculated To Be Tetrahedral, Whereas (CO)₄ Is Square Planar? A Molecular Orbital Analysis

Why Is (SiO)₄ Calculated To Be Tetrahedral, Whereas (CO)₄ Is Square Planar? A Molecular Orbital Analysis

Synthesis and Applications of Perfunctionalized Boron Clusters

Dehydrogenation of Perfluoroalkyl Ketones by Using a Recyclable Oxoammonium Salt

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Chemistry of the boron subhalides. Preparation, boron nuclear magnetic resonance, and thermal stability of tetraboron tetrachloride

Cited by 26 publications

References 45 publications

Why Is (SiO)4 Calculated To Be Tetrahedral, Whereas (CO)4 Is Square Planar? A Molecular Orbital Analysis

Why Is (SiO)4 Calculated To Be Tetrahedral, Whereas (CO)4 Is Square Planar? A Molecular Orbital Analysis

Synthesis and Applications of Perfunctionalized Boron Clusters

Dehydrogenation of Perfluoroalkyl Ket­ones by Using a Recyclable Oxoammonium Salt

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Product

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Why Is (SiO)₄ Calculated To Be Tetrahedral, Whereas (CO)₄ Is Square Planar? A Molecular Orbital Analysis

Why Is (SiO)₄ Calculated To Be Tetrahedral, Whereas (CO)₄ Is Square Planar? A Molecular Orbital Analysis

Dehydrogenation of Perfluoroalkyl Ketones by Using a Recyclable Oxoammonium Salt